Piezoelectric ceramic material, preparation method thereof and piezoelectric device

Abstract

The invention discloses a piezoelectric ceramic material, a preparation method thereof and a piezoelectric device, and belongs to the technical field of inorganic non-metallic materials, the chemical composition of the piezoelectric ceramic material is (1-a-b) Pb (Zr < 0.5 > Ti < 0.5 >) O < 3-b > Pb (Zn < 1 / 3 > Nb < 2 / 3 >) O < 3-a > Pb (Ni < 1 / 3 > Nb < 2 / 3 >) O < 3 + x wt% M + y wt% ZnO, wherein a is more than or equal to 0.04 and less than or equal to 0.08; 0.08 < = b < = 0.12; m is a sintering aid, x represents the mass percent of the sintering aid M in the mass of the ceramic matrix, and x is greater than or equal to 0 and less than or equal to 1; y represents the mass percent of ZnO in the mass of the ceramic matrix, and y is more than or equal to 0 and less than or equal to 1. According to the invention, the technical effects of high piezoelectric property, low sintering temperature and high Curie temperature are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic non-metallic materials, and in particular to a piezoelectric ceramic material and a preparation method thereof, and a piezoelectric device. Background Art

[0002] Piezoelectric ceramic materials are functional ceramic materials that can convert mechanical energy into electrical energy. Among them, PZT-based piezoelectric ceramics still dominate in actual production applications due to their advantages such as easy manufacturing, low cost, excellent electrical properties, and stable performance. With the rapid development of consumer electronics, smart homes, and automobiles, new requirements have been put forward for piezoelectric ceramics. Piezoelectric ceramics have new applications in acoustic compensation, touch pressing, motors, and other fields.

[0003] The high piezoelectric performance, low sintering temperature and high Curie temperature of piezoelectric ceramic materials are contradictory. Usually, the performance decreases when the sintering temperature is lowered. The piezoelectric coefficient of materials with high Curie temperature is usually lower. It is very important to ensure that the Curie temperature and sintering temperature meet the process use requirements and production requirements while ensuring the piezoelectric performance. Summary of the invention

[0004] The main purpose of the present invention is to provide a piezoelectric ceramic material and a preparation method thereof, and a piezoelectric device, aiming to solve the technical problem that existing piezoelectric materials are difficult to achieve high piezoelectric performance, low sintering temperature and high Curie temperature.

[0005] To achieve the above object, the present invention provides a piezoelectric ceramic material having a chemical composition of: (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-bPb(Zn 1 / 3 Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3+xwt%M+ywt%ZnO;

[0006] Among them, (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-b Pb(Zn 1 / 3 Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3 represents a ceramic matrix;

[0007] a represents Pb(Ni 1 / 3 Nb 2 / 3 ) the molar fraction of O3 in the ceramic matrix, 0.04≤a≤0.08;

[0008] b represents Pb(Zn 1 / 3 Nb2 / 3 ) the molar fraction of O3 in the ceramic matrix, 0.08≤b≤0.12;

[0009] M is a sintering aid, x represents the mass percentage of the sintering aid M to the mass of the ceramic matrix, 0≤x≤1;

[0010] y represents the mass percentage of ZnO in the mass of the ceramic matrix, 0≤y≤1.

[0011] In one embodiment, x and y satisfy 0<x+y≤1.

[0012] In one embodiment, the sintering aid M includes, by mass, 50-70 parts of Bi2O3, 10-30 parts of Sb2O3, 5-10 parts of Li2CO3, 3-8 parts of B2O3 and 2-7 parts of ZnO.

[0013] In one embodiment, the piezoelectric ceramic material is sintered at a temperature of 850-950° C. to form a sample, and the sample is polarized at 120° C. and 3 KV / mm. The piezoelectric coefficient d 33 >480pC / N.

[0014] In one embodiment, the piezoelectric ceramic material is sintered at a temperature of 850-950° C. to form a sample, and the sample is polarized at 120° C. and 3 KV / mm, and the Curie temperature Tc of the sample is ≥300° C.

[0015] In addition, to achieve the above object, the present invention also provides a method for preparing a piezoelectric ceramic material, which is used to prepare the piezoelectric ceramic material as described above, and the method comprises:

[0016] Weigh ceramic matrix raw materials according to chemical composition and mix them to obtain a mixed material;

[0017] Pre-burning the mixed material to obtain a synthetic material;

[0018] The sintering aid M and / or ZnO raw material are mixed and ground with the synthetic material to obtain a piezoelectric ceramic material.

[0019] In one embodiment, the sintering aid is prepared by the following steps:

[0020] The sintering aid raw materials are mixed uniformly, and the sintering aid M is obtained after melting, cooling, crushing and fine grinding in sequence.

[0021] In one embodiment, the melting temperature is 1150-1250°C.

[0022] In one embodiment, the pre-firing temperature is 800-850° C.; and / or the pre-firing treatment holding time is 2-4 hours.

[0023] In addition, to achieve the above objective, an embodiment of the present invention further provides a piezoelectric device, wherein the piezoelectric device includes the piezoelectric ceramic material as described above.

[0024] The piezoelectric ceramic material provided by the present invention has a chemical composition of (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-bPb(Zn 1 / 3Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3+xwt%M+ywt%ZnO, on the basis of PZT-based ceramics, a quaternary piezoelectric ceramic system is constructed by composite doping of Zn, Ni and Nb to form a relaxor ferroelectric with a composite perovskite structure. Compared with ordinary ferroelectrics, relaxor ferroelectrics exhibit diffuse phase transition and frequency dispersion characteristics. The diffuse phase transition causes a lower capacitance change rate, which greatly improves the piezoelectric properties of the PZT-based ceramics. In addition, the addition amount of PZN and PNN is controlled so that the decrease in Curie temperature is not obvious. The sintering temperature can be effectively reduced by adding sintering aids M and ZnO. Therefore, the piezoelectric ceramic material can be sintered at a lower temperature and has excellent piezoelectric properties and a higher Curie temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present drawings or related technologies, the drawings required for use in the embodiments or related technical descriptions will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present drawings. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0026] Figure 1 A schematic diagram of a process for preparing a piezoelectric ceramic material according to an embodiment of the present invention;

[0027] Figure 2 This is a SEM image of the piezoelectric ceramic material of an embodiment of the present invention;

[0028] Figure 3 The figure is a microscope photograph of a multilayer piezoelectric ceramic slice prepared by using the piezoelectric ceramic material according to an embodiment of the present invention.

[0029] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0030] It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention.

[0031] Hereinafter, the piezoelectric ceramic material and its preparation method, and the implementation mode of the piezoelectric device of the present invention are specifically disclosed in detail with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structure are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present invention, and are not intended to limit the subject matter described in the claims.

[0032] "Scope" disclosed in the present invention is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3,4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0033] In order to make the above-mentioned objects, features and advantages of the present invention more clearly understood, the technical solutions of the present invention are further described below in conjunction with the accompanying drawings and embodiments. However, the present invention is not limited to the embodiments listed, and should also include any other known changes within the scope of the rights claimed by the present invention.

[0034] With the rapid development of consumer electronics, smart home and automobile fields, new requirements have been put forward for piezoelectric ceramics, and piezoelectric ceramics have new applications in acoustic compensation, touch pressing, motors and other fields. On the one hand, the consumer electronics field, such as headphones and mobile phones, has put forward higher requirements for the miniaturization of product size, which requires the material to meet the requirements of high performance in a small size; on the other hand, product assembly processes such as reflow soldering and injection molding have put forward new requirements for the temperature resistance of materials, which requires piezoelectric ceramic materials to have a high Curie temperature. In addition, due to environmental and cost considerations, the sintering temperature of piezoelectric ceramic materials is required to be low to prevent the volatilization of lead in the production process and reduce the cost of internal electrodes when producing multilayer piezoelectric ceramics.

[0035] Based on this, the embodiment of the present invention provides a piezoelectric ceramic material, the chemical composition of which is: (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-bPb(Zn 1 / 3 Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3+xwt%M+ywt%ZnO;

[0036] Among them, (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-b Pb(Zn 1 / 3 Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3 represents a ceramic matrix;

[0037] a represents Pb(Ni 1 / 3 Nb 2 / 3 ) the molar fraction of O3 in the ceramic matrix, 0.04≤a≤0.08;

[0038] b represents Pb(Zn 1 / 3 Nb 2 / 3 ) the molar fraction of O3 in the ceramic matrix, 0.08≤b≤0.12;

[0039] M is a sintering aid, x represents the mass percentage of the sintering aid M to the mass of the ceramic matrix, 0≤x≤1;

[0040] y represents the mass percentage of ZnO in the mass of the ceramic matrix, 0≤y≤1.

[0041] It is understandable that Pb(Zr 0.5 Ti 0.5)O3 represents the lead zirconate titanate component, which is the main component in the ceramic matrix. The doping of Zn, Ni, and Nb can form Pb(Zn) represented by PZN. 1 / 3 Nb 2 / 3 )O3 components and Pb(Ni 1 / 3 Nb 2 / 3 )O3 component. Lead zirconate titanate has an ABO3 perovskite structure, in which the A position is lead ion, and the B position is zirconium ion and titanium ion. The doping of Zn, Ni, and Nb elements occurs at the B position, and the doping amount of different elements will affect the degree of oxygen octahedral lattice distortion.

[0042] This embodiment controls the doping amount of Ni and Nb elements by limiting the size of a. Specifically, 0.04≤a≤0.08, for example, a can be 0.04, 0.05, 0.06, 0.07, 0.08, etc. The ionic radius of nickel ions is smaller than that of zirconium ions and titanium ions, and the ionic radius of niobium ions is similar to that of titanium ions. The doping of nickel ions will cause local contraction of the lattice, and the doping of niobium ions has little effect on the lattice distortion. The larger a is, the more Ni and Nb elements are doped. Appropriate amounts of Ni and Nb elements doping can improve the piezoelectric properties of piezoelectric ceramic materials, while excessive doping may lead to excessive defects, hindering the movement of domain walls and polarization reversal, resulting in a decrease in piezoelectric performance and an excessive decrease in Curie temperature.

[0043] This embodiment controls the doping amount of Zn and Nb elements by limiting the size of b. Specifically, 0.08≤b≤0.12, for example, b can be 0.08, 0.09, 0.10, 0.11, 0.12, etc. The ionic radius of zinc ions is smaller than that of zirconium ions and titanium ions, and the doping of zinc ions will cause local contraction of the lattice. The larger the b, the more the doping amount of Zn and Nb elements. The appropriate amount of Zn and Nb doping can improve the piezoelectric properties of piezoelectric ceramic materials, while excessive doping may lead to excessive defects, hindering the movement of domain walls and polarization reversal, resulting in a decrease in piezoelectric performance and an excessive decrease in Curie temperature.

[0044] The piezoelectric ceramic material of this embodiment also contains sintering aid M and / or ZnO, and ZnO can also play the role of a sintering aid. It can be understood that by adding sintering aids M and ZnO, the sintering temperature can be further effectively reduced. If the addition amount is too low, the sintering temperature cannot be effectively reduced. However, if the addition amount is too high, the piezoelectric performance will be significantly deteriorated. By limiting the addition amount of sintering aids M and ZnO within a suitable range, 0≤x≤1, that is, the addition amount of sintering aid M is at most 1wt% of the mass of the ceramic matrix, 0≤y≤1, that is, the addition amount of ZnO is at most 1wt% of the mass of the ceramic matrix, the sintering temperature can be reduced without excessively affecting the piezoelectric properties of the piezoelectric ceramic material after sintering.

[0045] In some feasible implementations, x and y satisfy 0<x+y≤1, that is, x and y are not zero at the same time, for example, the value of x+y is 0.1, 0.2, 0.3, 0.5, 0.8, 1, etc. In this way, it is ensured that at least one sintering aid exists in the piezoelectric ceramic material to meet the requirement for low sintering temperature.

[0046] In some feasible embodiments, the sintering aid M includes 50-70 parts of Bi2O3, 10-30 parts of Sb2O3, 5-10 parts of Li2CO3, 3-8 parts of B2O3 and 2-7 parts of ZnO by weight. The amount of Bi2O3 added to the sintering aid M is 50-70 parts, for example, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, etc. The amount of Sb2O3 added to the sintering aid M is 10-30 parts, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc. The amount of Li2CO3 added to the sintering aid M is 5-10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc. The amount of B2O3 added to the sintering aid M is 3-8 parts, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc. The amount of ZnO added to the sintering aid M is 2-7 parts, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, etc. It can be understood that the composite use of Bi2O3, Sb2O3, Li2CO3, B2O3 and ZnO can form a synergistic effect, and the effect of reducing the sintering temperature is more obvious compared with a single component sintering aid.

[0047] In some feasible implementations, the piezoelectric ceramic material is sintered at a temperature of 850-950° C. to prepare a sample, and the sample is polarized at 120° C. and 3 KV / mm. The piezoelectric coefficient d 33 >480pC / N, the Curie temperature Tc of the sample is ≥300℃. It is understandable that the sintering temperature of most piezoelectric ceramic materials is about 1000℃. In this embodiment, by adjusting the composition and adding sintering aids, the powdered piezoelectric ceramic material can be sintered into porcelain at a temperature of 850-950℃ to obtain a fired sample. This sample can be a disc sample, which is prepared by powder granulation, debinding, sintering, polarization treatment, and then the disc performance test is performed to measure the piezoelectric coefficient d 33>480pC / N, for example, 500pC / N, 510pC / N, 520pC / N, 530pC / N, 540pC / N, 550pC / N, etc., and the measured Curie temperature Tc ≥300°C, for example, 300°C, 305°C, 310°C, 315°C, 320°C, 325°C, etc. If the piezoelectric coefficient is too low, the piezoelectric performance will be poor, and it will be difficult to meet the requirements for piezoelectric properties after the piezoelectric device is made. If the Curie temperature of the piezoelectric ceramic is too low, it is easy to depolarize at high temperature, resulting in poor performance stability of the ceramic. Therefore, the piezoelectric ceramic material of this embodiment can take into account the requirements of high piezoelectric performance, low sintering temperature, and high Curie temperature.

[0048] The piezoelectric ceramic material of this embodiment, on the basis of PZT-based ceramics, constructs a quaternary piezoelectric ceramic system through the composite doping of Zn, Ni, and Nb to form a relaxor ferroelectric with a composite perovskite structure. Compared with ordinary ferroelectrics, the relaxor ferroelectric exhibits diffuse phase transition and frequency dispersion characteristics. The diffuse phase transition causes a lower capacitance change rate, which greatly improves the piezoelectric properties of the PZT-based ceramics. In addition, the addition amounts of PZN and PNN are controlled so that the Curie temperature is not significantly reduced. The sintering temperature can be effectively reduced by adding sintering aids M and ZnO. Therefore, the piezoelectric ceramic material can be sintered at a lower temperature and has excellent piezoelectric properties and a higher Curie temperature.

[0049] The present invention provides a method for preparing a piezoelectric ceramic material, which is used to prepare the piezoelectric ceramic material described in the above embodiment. Figure 1 , Figure 1 The present invention is a schematic diagram of a method for preparing a piezoelectric ceramic material according to an embodiment of the present invention.

[0050] In this embodiment, the preparation method of the piezoelectric ceramic material includes:

[0051] Step S10, weighing ceramic matrix raw materials according to chemical composition, and mixing to obtain a mixed material;

[0052] The ceramic matrix raw material is weighed according to the proportion in the chemical composition. The ceramic matrix raw material can be any Pb source, Zr source, Ti source, Zn source, Nb source, Ni source, such as oxides of the above elements. Optionally, deionized water is added to the ceramic matrix raw material, and zirconium balls are used as grinding media for dispersion grinding to obtain a uniformly mixed mixture.

[0053] Step S20, pre-burning the mixed material to obtain a synthetic material;

[0054] It is understandable that after the mixed material is obtained, it can be dried and sieved. Then the sieved mixed material is placed in a crucible for pre-calcination to obtain a synthetic material. The pre-calcination treatment can remove organic matter and moisture in the mixed material, improve the purity of the mixed material, and eliminate cracks and holes that may appear during the sintering process, thereby improving the density of the ceramic body.

[0055] Optionally, the temperature of the pre-firing treatment is 800-850°C, for example, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, etc. If the pre-firing temperature is too low, it may lead to insufficient pre-reaction between the components in the mixed material, which is not conducive to improving the density of the ceramic body. If the pre-firing temperature is too high, it may lead to the generation of secondary recrystallization, deteriorate the piezoelectric properties of the piezoelectric ceramic material, or may also cause residual pores. The holding time of the pre-firing treatment is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, 4h, etc. If the pre-firing holding time is too short, the pre-firing reaction is insufficient, and if the holding time is too long, over-firing may occur, resulting in performance degradation. An appropriate pre-firing temperature can promote solid-phase reaction, and combined with an appropriate holding time, the performance of piezoelectric ceramics can be improved.

[0056] Step S30, taking a sintering aid M and / or a ZnO raw material, mixing and grinding with the synthetic material to obtain a piezoelectric ceramic material.

[0057] It is understandable that the piezoelectric ceramic material as described above can be obtained by grinding and dispersing the synthesized material together with the sintering aid M and / or ZnO raw material. The piezoelectric ceramic material is a uniformly dispersed ultrafine material.

[0058] Optionally, the sintering aid raw materials are mixed evenly, and the sintering aid M is obtained after melting, cooling, crushing and fine grinding in sequence. Take the sintering aid raw materials Bi2O3, Sb2O3, Li2CO3, B2O3 and ZnO, and mix them according to the mass ratio. The melting temperature can be 1150-1250°C, for example, 1150°C, 1180°C, 1200°C, 1230°C, 1250°C, etc. Finely grind the sintering aid M in the form of ultrafine nano powder. Grind and disperse the sintering aid M and / or ZnO together with the synthetic material to obtain a uniformly dispersed piezoelectric ceramic material. The piezoelectric ceramic material prepared in this embodiment is observed microscopically, Figure 2 The SEM (Scanning Electron Microscope) image of the piezoelectric ceramic material of this embodiment is shown in FIG. Figure 2 As shown, the piezoelectric ceramic material prepared in this embodiment appears as a uniformly dispersed powder under an electron microscope.

[0059] In this embodiment, piezoelectric ceramic materials are prepared by pre-firing and other processes. On the basis of PZT-based ceramics, a quaternary piezoelectric ceramic system is constructed by composite doping of Zn, Ni, and Nb to form a relaxor ferroelectric with a composite perovskite structure. Compared with ordinary ferroelectrics, relaxor ferroelectrics exhibit diffuse phase transition and frequency dispersion characteristics. The diffuse phase transition causes a lower capacitance change rate, which greatly improves the piezoelectric properties of the PZT-based ceramics. In addition, the addition amounts of PZN and PNN are controlled so that the Curie temperature is not significantly reduced. The sintering temperature can be effectively reduced by adding sintering aids M and ZnO. Therefore, the piezoelectric ceramic material can be sintered at a lower temperature and has excellent piezoelectric properties and a higher Curie temperature.

[0060] The embodiment of the present invention also provides a piezoelectric device, including the piezoelectric ceramic material described in the above embodiment. It is understandable that the piezoelectric device can be prepared by sintering the above piezoelectric ceramic material at 850-950°C, and can be widely used in piezoelectric acoustic devices, tactile feedback, piezoelectric motors and other devices. In a feasible implementation, the piezoelectric device is a multilayer piezoelectric ceramic formed by a tape casting process, in which silver paste is used as the inner and outer electrodes. Figure 3 is a microscope photograph of a multilayer piezoelectric ceramic slice prepared using the piezoelectric ceramic material of this embodiment, Figure 3 Each layer of piezoelectric ceramic is connected by silver paste, and the multilayer piezoelectric ceramic has a very large advantage in terms of production cost. Compared with the products circulating on the market, the piezoelectric ceramic material and piezoelectric device prepared in this embodiment can maintain higher piezoelectric performance and higher Curie temperature at a lower sintering temperature. On the basis of meeting the new requirements for the temperature resistance of materials such as reflow soldering and injection molding, the production cost can be significantly reduced, especially the production cost of multilayer piezoelectric products, and it has a very broad application prospect in the preparation of high-performance and high-temperature-resistant piezoelectric devices.

[0061] The present invention is described in detail below with reference to specific embodiments.

[0062] Example 1

[0063] The chemical composition of piezoelectric ceramic materials is: 0.86Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.04Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0064] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0065] Example 2

[0066] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0067] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0068] Example 3

[0069] The chemical composition of piezoelectric ceramic materials is: 0.82Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.08Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0070] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0071] Example 4

[0072] The chemical composition of piezoelectric ceramic materials is: 0.86Pb(Zr 0.5 Ti 0.5 )O3-0.08Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0073] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0074] Example 5

[0075] The chemical composition of piezoelectric ceramic materials is: 0.82Pb(Zr 0.5 Ti 0.5 )O3-0.12Pb(Zn 1 / 3 Nb 2 / 3)O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0076] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0077] Example 6

[0078] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.5wt%ZnO.

[0079] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0080] Example 7

[0081] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+1wt%ZnO.

[0082] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0083] Example 8

[0084] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.5wt%M.

[0085] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0086] Example 9

[0087] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+1wt%M.

[0088] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0089] Example 10

[0090] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.5wt%M+0.5wt%ZnO.

[0091] Sintering aid M: Bi2O3 64 parts, Sb2O3 17 parts, Li2CO3 9 parts, B2O3 5 parts, ZnO 5 parts.

[0092] Embodiment 11

[0093] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3 Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0094] Sintering aid M: Bi2O3 70 parts, Sb2O3 12 parts, Li2CO3 7 parts, B2O3 5 6 parts, ZnO 5 parts.

[0095] Example 12

[0096] The chemical composition of piezoelectric ceramic materials is: 0.84Pb(Zr 0.5 Ti 0.5 )O3-0.10Pb(Zn 1 / 3 Nb 2 / 3 )O3-0.06Pb(Ni 1 / 3Nb 2 / 3 )O3+0.25wt%M+0.25wt%ZnO.

[0097] Sintering aid M: Bi2O3 57 parts, Sb2O3 25 parts, Li2CO3 5 parts, B2O3 5 10 parts, ZnO3 parts.

[0098] In addition, Examples 1-12 and Comparative Example 1 were sintered at 930° C. for 4 hours. Piezoelectric performance tests were performed on Examples 1-12 and Comparative Example 1, and the test results are shown in Table 1 below.

[0099] Table 1

[0100]

[0101] As can be seen from Table 1, Comparative Example 1 failed to be sintered at 930° C. because no sintering aid M and ZnO were added. The reason may be that the sintering temperature of the piezoelectric ceramic material of this component is too high, higher than 930° C. However, Examples 1-12 within the parameter range of this embodiment can all be sintered into porcelain at 930° C., and have a higher Curie temperature and a larger piezoelectric constant, and have excellent piezoelectric properties.

[0102] The serial numbers of the above embodiments of the present invention are for description only and do not represent the advantages or disadvantages of the embodiments.

[0103] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A piezoelectric ceramic material, characterized in that: The chemical composition of the piezoelectric ceramic material is: (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-bPb(Zn 1 / 3 Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3+xwt%M+ywt%ZnO; Among them, (1-ab)Pb(Zr 0.5 Ti 0.5 )O3-b Pb(Zn 1 / 3 Nb 2 / 3 )O3-aPb(Ni 1 / 3 Nb 2 / 3 )O3 represents a ceramic matrix; a represents Pb(Ni 1 / 3 Nb 2 / 3 ) the molar fraction of O3 in the ceramic matrix, 0.04≤a≤0.08; b represents Pb(Zn 1 / 3 Nb 2 / 3 ) the molar fraction of O3 in the ceramic matrix, 0.08≤b≤0.12; M is a sintering aid, x represents the mass percentage of the sintering aid M to the mass of the ceramic matrix, 0≤x≤1; y represents the mass percentage of ZnO in the mass of the ceramic matrix, 0≤y≤1.

2. The piezoelectric ceramic material according to claim 1, characterized in that: The x and y satisfy 0<x+y≤1.

3. The piezoelectric ceramic material according to claim 1, characterized in that: In terms of mass fractions, the sintering aid M includes 50-70 parts of Bi2O3, 10-30 parts of Sb2O3, 5-10 parts of Li2CO3, 3-8 parts of B2O3 and 2-7 parts of ZnO.

4. The piezoelectric ceramic material according to claim 1, characterized in that: The piezoelectric ceramic material is sintered at a temperature of 850-950° C. to prepare a sample, and the sample is polarized at 120° C. and 3 KV / mm. The piezoelectric coefficient d 33 >480pC / N.

5. The piezoelectric ceramic material according to claim 1, characterized in that: The piezoelectric ceramic material is sintered at a temperature of 850-950° C. to prepare a sample, and the sample is polarized at 120° C. and 3 KV / mm. The Curie temperature Tc of the sample is ≥300° C.

6. A method for preparing a piezoelectric ceramic material, characterized in that: For preparing the piezoelectric ceramic material according to any one of claims 1 to 5, the method comprises: Weigh ceramic matrix raw materials according to chemical composition and mix them to obtain a mixed material; Pre-burning the mixed material to obtain a synthetic material; The sintering aid M and / or ZnO raw material are mixed and ground with the synthetic material to obtain a piezoelectric ceramic material.

7. The method for preparing a piezoelectric ceramic material according to claim 6, characterized in that: The sintering aid is prepared by the following steps: The sintering aid raw materials are mixed uniformly, and the sintering aid M is obtained after melting, cooling, crushing and fine grinding in sequence.

8. The method for preparing a piezoelectric ceramic material according to claim 7, characterized in that: The melting temperature is 1150-1250°C.

9. The method for preparing a piezoelectric ceramic material according to claim 6, characterized in that: The temperature of the pre-sintering treatment is 800-850° C.; and / or the holding time of the pre-sintering treatment is 2-4 hours.

10. A piezoelectric device, characterized in that: The piezoelectric device comprises the piezoelectric ceramic material according to any one of claims 1 to 5.

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