A piezoelectric ceramic material and its preparation method and piezoelectric device

Abstract

The present application discloses a piezoelectric ceramic material and a preparation method thereof and a piezoelectric device. The piezoelectric ceramic material has the chemical formula: 0.03Bi(Zn 1 / 2 Ti 1 / 2 )O3‑0.07Pb(Mn 1 / 3 Nb 2 / 3 )O3‑0.9Pb(Zr 0.46 Ti 0.54 The piezoelectric ceramic material provided in the present application can ensure that the sintered product has good piezoelectric properties, a high Curie temperature and low loss at a relatively low sintering temperature.

Description

Technical Field

[0001] The present application relates to the technical field of piezoelectric materials, and more specifically, 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 and electrical energy into each other. 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. However, the sintering temperature of traditional lead-based piezoelectric ceramics is relatively high, generally around 1100℃ to 1300℃. In the prior art, there is a method of adding low-melting-point oxides to promote liquid phase sintering and reduce the sintering temperature of the material, but this will also reduce the piezoelectric properties of the material and cause large losses. Summary of the invention

[0003] One object of the present application is to provide a new technical solution for a piezoelectric ceramic material and a method for preparing the same, and a piezoelectric device.

[0004] According to the first aspect of the present application, a piezoelectric ceramic material is provided, the chemical formula of which is: 0.03Bi(Zn 1 / 2 Ti 1 / 2 )O3-0.07Pb(Mn 1 / 3 Nb 2 / 3 )O3-0.9Pb(Zr 0.46 Ti 0.54 )O3.

[0005] Optionally, the piezoelectric ceramic material further includes a sintering aid, and the sintering aid is one or more of LiBiO2, Fe2O3, NiO and ZnO.

[0006] Optionally, the sintering aid is added in an amount of 0-0.5 wt %.

[0007] Optionally, the LiBiO2 is synthesized from Li2CO3 and Bi2O3 using a solid phase method.

[0008] Optionally, the Pb source is PbO or Pb3O4, the Zr source is ZrO2, the Ti source is TiO2, the Mn source is MnO2, the Zn source is ZnO, and the Nb source is Nb2O5.

[0009] Optionally, the sintering temperature of the piezoelectric ceramic material is 850°C-950°C.

[0010] Optionally, the piezoelectric ceramic material has an electromechanical coupling coefficient Kp≥0.6, a Curie temperature Tc>330° C., and a dielectric loss tanδ≤0.5%.

[0011] According to a second aspect of the present application, there is provided a method for preparing the piezoelectric ceramic material as described in the first aspect, comprising:

[0012] Weigh the raw materials according to the ratio of the chemical formula, add deionized water to the raw materials, and perform dispersion and grinding to obtain a uniformly mixed material I;

[0013] After drying and sieving material I, pre-calcining at a certain pre-calcining temperature to obtain synthetic material II;

[0014] The synthesized material II is ground and dispersed to obtain the piezoelectric ceramic material.

[0015] Optionally, the pre-firing temperature is 750-850°C.

[0016] Optionally, zirconium balls are used as grinding media for dispersion grinding.

[0017] According to a third aspect of the present application, a piezoelectric device is provided, which is prepared using the piezoelectric ceramic material described in the first aspect.

[0018] According to an embodiment of the present application, the piezoelectric ceramic material provided by the present application not only has a lower sintering temperature, but also can ensure that the sintered product has good piezoelectric properties, a higher Curie temperature and lower loss.

[0019] Other features and advantages of the present application will become apparent from the following detailed description of exemplary embodiments of the present application with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the application and, together with the description, serve to explain the principles of the application.

[0021] Figure 1 This is a surface SEM photograph of a piezoelectric ceramic device prepared using the piezoelectric ceramic material provided in this application.

[0022] Figure 2 yes Figure 1 Cross-sectional SEM photograph of the piezoelectric ceramic device in. DETAILED DESCRIPTION

[0023] Various exemplary embodiments of the present application will now be described in detail with reference to the accompanying drawings. It should be noted that unless otherwise specifically stated, the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present application.

[0024] The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the present application, its application, or uses.

[0025] Technologies, methods, and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods, and equipment should be considered as part of the specification.

[0026] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0027] It should be noted that like reference numerals and letters refer to similar items in the following figures, and therefore, once an item is defined in one figure, it need not be further discussed in subsequent figures.

[0028] According to the first aspect of the present application, a piezoelectric ceramic material is provided, the chemical formula of which is: 0.03Bi(Zn 1 / 2 Ti 1 / 2 )O3-0.07Pb(Mn 1 / 3 Nb 2 / 3 )O3-0.9Pb(Zr 0.46 Ti 0.54 )O3.

[0029] Specifically, in this embodiment, the piezoelectric ceramic material is mainly composed of Bi(Zn 1 / 2 Ti 1 / 2 )O3-Pb(Mn 1 / 3 Nb 2 / 3 )O3-Pb(Zr 0.46 Ti 0.54 )O3, among which the doping of Mn and Nb elements can improve the piezoelectric properties of pure PZT and reduce the loss of piezoelectric ceramic materials, while Bi(Zn 1 / 2 Ti 1 / 2 ) The addition of O3 can further reduce the sintering temperature of the material. The reduction of the sintering temperature of the piezoelectric ceramic material not only reduces the volatilization of Pb, but also enables more product design requirements to be met when preparing piezoelectric devices, such as multilayer piezoelectric motors, ultrasonic transducers and other devices.

[0030] When preparing the above-mentioned piezoelectric ceramic material, Bi(Zn 1 / 2 Ti 1 / 2 )O3、Pb(Mn 1 / 3 Nb 2 / 3 )O3 and Pb(Zr 0.46 Ti 0.54) The molar mass ratio of O3 can be adjusted to 0.03:0.07:0.9, so that the prepared piezoelectric ceramic material has better piezoelectric properties and ensures a lower sintering temperature. In addition, the prepared piezoelectric ceramic material also has a higher Curie temperature and lower loss, reducing the material cost.

[0031] Optionally, the piezoelectric ceramic material further includes a sintering aid, and the sintering aid is one or more of LiBiO2, Fe2O3, NiO and ZnO.

[0032] Specifically, in this embodiment, the piezoelectric ceramic material also includes a sintering aid to further reduce the sintering temperature of the piezoelectric ceramic material and ensure that its piezoelectric properties are not affected. The type of additive can be one or more of LiBiO2, Fe2O3, NiO and ZnO. All of the above additives are conventional materials with high stability and can be used in mass production. In addition, the sintering aid cooperates with the Bi(Zn 1 / 2 Ti 1 / 2 )O3 components can form liquid phase sintering during sintering and enhance the sintering driving force, that is, LiBiO2, NiO and ZnO can reduce the sintering temperature of the material without significantly reducing the piezoelectric properties of the material.

[0033] Optionally, the sintering aid is added in an amount of 0-0.5 wt %.

[0034] Specifically, in practical applications, excessive addition of sintering aids can lead to a sharp deterioration in the piezoelectric properties of the material. Setting the addition ratio within 0.5wt%, such as 0.1wt%, 0.3wt%, 0.4wt%, etc., can ensure the piezoelectric performance while lowering the sintering temperature of the piezoelectric ceramic material.

[0035] Optionally, the Pb source is PbO or Pb3O4, the Zr source is ZrO2, the Ti source is TiO2, the Mn source is MnO2, the Zn source is ZnO, the Nb source is Nb2O5, and the Bi source is LiBiO2.

[0036] Specifically, in the actual preparation process, the raw materials for preparing piezoelectric ceramic materials can be selected from any Pb, Zr, Ti, Mn, Nb, Ni, Zn, Li, and Bi sources. In actual production, in order to ensure the stability of production, the Pb source uses PbO or Pb3O4, the Zr source uses ZrO2, the Ti source uses TiO2, the Mn source uses Mn2O3, the Zn source uses ZnO, and the Nb source uses Nb2O5.

[0037] Optionally, the sintering temperature of the piezoelectric ceramic material is 850°C-950°C.

[0038] Specifically, in this embodiment, the sintering temperature of the piezoelectric ceramic material is 850°C-950°C, which is significantly lower than the sintering temperature of the piezoelectric ceramic material in the prior art, which is usually above 1100°C. The reduction in sintering temperature can meet the preparation requirements of some devices with low sintering temperature requirements in the process of preparing multilayer piezoelectric ceramics using the piezoelectric ceramic material in this application.

[0039] For example, in one embodiment, when using piezoelectric ceramic materials to prepare multilayer piezoelectric ceramic devices, it is usually desirable to use silver internal electrodes in order to reduce costs. However, since the melting point of silver is 962°C, the piezoelectric ceramic materials in the prior art cannot meet this requirement. The sintering temperature of the piezoelectric ceramic material provided in this application is only 850°C-950°C, and it can match the silver electrode when the multilayer piezoelectric ceramic device is sintered, so that it has a wide range of applications in multilayer piezoelectric motors, ultrasonic transducers and other devices, reducing material costs.

[0040] Optionally, the piezoelectric ceramic material has an electromechanical coupling coefficient Kp≥0.6, a Curie temperature>330° C., and a dielectric loss tanδ≤0.5%.

[0041] Specifically, in the present embodiment, the piezoelectric ceramic material has a higher electromechanical coupling coefficient, a higher Curie temperature and a lower dielectric loss. When the piezoelectric ceramic material is sintered into a piezoelectric device, the piezoelectric performance of the piezoelectric device can be further guaranteed and the material cost can be reduced.

[0042] According to a second aspect of the present application, there is provided a method for preparing the piezoelectric ceramic material as described in the first aspect, comprising:

[0043] S01: weigh the raw materials according to the ratio of the chemical formula, add deionized water to the raw materials, and disperse and grind them to obtain a uniformly mixed material I.

[0044] In this step, after weighing the raw materials according to the set ratio, deionized water can be added to the raw materials, and after the raw materials are synthesized by the solid phase method, zirconium balls are used as grinding media to disperse and grind them so that the raw materials are evenly mixed.

[0045] S02: After drying and sieving material I, pre-burning and keeping warm at a certain pre-burning temperature to obtain synthetic material II.

[0046] In this step, material I is further processed, that is, it is dried and sieved, and is placed in a crucible for pre-calcination at 750-850° C. and heat preservation for 2-4 hours.

[0047] S03: Grind and disperse the synthesized material II to obtain the piezoelectric ceramic material.

[0048] Optionally, the pre-firing temperature is 750-850° C., and the holding time is 2-4 hours.

[0049] Optionally, zirconium balls are used as grinding media for dispersion grinding. The obtained piezoelectric ceramic material can be further sintered to form a piezoelectric ceramic product.

[0050] According to the third aspect of the present application, reference Figure 1 to Figure 2 , provides a piezoelectric device, which is prepared using the piezoelectric ceramic material described in the first aspect.

[0051] Specifically, in this embodiment, the piezoelectric device is made of the piezoelectric ceramic material provided in the first aspect of the present application, and the surface photograph of the manufactured piezoelectric device is referenced to Figure 1 , cross-section photo reference Figure 2 . Since the piezoelectric ceramic material provided by the present application has a lower sintering temperature and a higher Curie temperature, as well as a larger electromechanical coupling coefficient and a lower dielectric loss, the performance stability of the piezoelectric ceramic device is guaranteed, so that it can be applied to the preparation of a variety of piezoelectric devices. For example, multilayer piezoelectric motors, ultrasound and other fields. In the actual production process, the low sintering temperature reduces the volatilization of lead vapor, reducing environmental pollution and manufacturing costs.

[0052] In order to make the technical effects of the present application more clear, a number of embodiments and comparative examples are provided below.

[0053] Embodiment 1:

[0054] In this embodiment, the weight of each raw material is as follows: 0.03Bi(Zn 1 / 2 Ti 1 / 2 )O3-0.07Pb(Mn 1 / 3 Nb 2 / 3 )O3-0.9Pb(Zr 0.46 Ti 0.54 )O3 is proportioned and 0.05wt% of sintering aid LiBiO2 is added, that is, 100g of the above materials are taken, among which 67.32g of Pb3O4, 15.49g of ZrO2, 12.15g of TiO2, 0.62g of MnO2, 1.88g of Nb2O5, 2.12g of Bi2O3, 0.37g of ZnO and 0.05g of LiBiO2 are weighed, and the piezoelectric ceramic material is prepared according to the preparation method provided in the second aspect of the present application, and its sintering temperature is measured to be 950°C.

[0055] The obtained piezoelectric ceramic material was granulated to prepare discs, which were sintered at 950°C. The electrodes on the formed discs were polarized at 120°C and 3KV / mm. The disc performance was tested and the piezoelectric properties were measured to be d33=345pC / N, dielectric constant=1644, Kp=0.64, and tanδ=0.3%.

[0056] Embodiment 2:

[0057] In this embodiment, 0.1wt% of the sintering aid LiBiO2 is added, that is, the above materials with a total weight of 100g are taken, of which 67.28g of Pb3O4, 15.48g of ZrO2, 12.15g of TiO2, 0.62g of MnO2, 1.88g of Nb2O5, 2.12g of Bi2O3, 0.37g of ZnO, and 0.10g of LiBiO2 are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 940°C, and the piezoelectric properties of the sintered discs are d33=342pC / N, the dielectric constant=1522, Kp=0.63, and tanδ=0.35%.

[0058] Embodiment 3:

[0059] In this embodiment, 0.2wt% of the sintering aid LiBiO2 is added, that is, the above materials with a total weight of 100g are taken, of which 67.21g of Pb3O4, 15.47g of ZrO2, 12.13g of TiO2, 0.62g of MnO2, 1.88g of Nb2O5, 2.12g of Bi2O3, 0.37g of ZnO, and 0.20g of LiBiO2 are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 910°C, and the piezoelectric properties of the sintered discs are d33=335pC / N, the dielectric constant=1471, Kp=0.63, and tanδ=0.4%.

[0060] Embodiment 4:

[0061] In this embodiment, 0.3wt% of the sintering aid LiBiO2 is added, that is, the above materials with a total weight of 100g are taken, of which 67.15g of Pb3O4, 15.45g of ZrO2, 12.12g of TiO2, 0.61g of MnO2, 1.88g of Nb2O5, 2.12g of Bi2O3, 0.37g of ZnO, and 0.30g of LiBiO2 are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 890°C, and the piezoelectric properties of the sintered disc are d33=330pC / N, the dielectric constant=1430, Kp=0.62, and tanδ=0.45%.

[0062] Embodiment 5:

[0063] In this embodiment, 0.5wt% of the sintering aid LiBiO2 is added, that is, the above materials with a total weight of 100g are taken, of which 67.01g of Pb3O4, 15.42g of ZrO2, 12.10g of TiO2, 0.61g of MnO2, 1.87g of Nb2O5, 2.11g of Bi2O3, 0.37g of ZnO, and 0.50g of LiBiO2 are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 850°C, and the piezoelectric properties of the sintered disc are d33=315pC / N, the dielectric constant=1350, Kp=0.62, and tanδ=0.5%.

[0064] Embodiment 6:

[0065] In this embodiment, 0.3wt% of sintering aid LiBiO2 and 0.2wt% of sintering aid ZnO are added, that is, the above materials with a total weight of 100g are taken, of which 67.01g of Pb3O4, 15.42g of ZrO2, 12.10g of TiO2, 0.61g of MnO2, 1.87g of Nb2O5, 2.11g of Bi2O3, 0.57g of ZnO, and 0.30g of LiBiO2 are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 850°C, and the piezoelectric properties of the sintered disc are d33=320pC / N, the dielectric constant=1377, Kp=0.63, and tanδ=0.45%.

[0066] Embodiment 7:

[0067] In this embodiment, 0.3wt% of sintering aid LiBiO2 and 0.2wt% of sintering aid NiO are added, that is, the above materials with a total weight of 100g are taken, of which 67.01g of Pb3O4, 15.42g of ZrO2, 12.10g of TiO2, 0.61g of MnO2, 1.87g of Nb2O5, 2.11g of Bi2O3, 0.37g of ZnO, 0.30g of LiBiO2, and 0.2g of NiO are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 850°C, and the piezoelectric properties of the sintered disc are d33=324pC / N, the dielectric constant=1402, Kp=0.63, and tanδ=0.4%.

[0068] Embodiment 8:

[0069] In this embodiment, 0.3wt% of sintering aid LiBiO2, 0.05wt% of sintering aid NiO, and 0.05wt% of sintering aid Fe2O3 are added, that is, 100g of the above materials are taken, among which 67.08g of Pb3O4, 15.44g of ZrO2, 12.11g of TiO2, 0.61g of MnO2, 1.88g of Nb2O5, and 2 .12g of Bi2O3, 0.37g of ZnO, 0.30g of LiBiO2, 0.05g of Fe2O3, and 0.05g of NiO, and after the piezoelectric ceramic material is prepared according to the preparation method in Example 1, the sintering temperature is 860°C, and the piezoelectric properties of the sintered disc are d33=320pC / N, the dielectric constant=1377, Kp=0.64, and tanδ=0.5%.

[0070] Embodiment 9:

[0071] In this embodiment, 0.3wt% of sintering aid LiBiO2, 0.1wt% of sintering aid ZnO, and 0.1wt% of sintering aid NiO are added, that is, the above materials with a total weight of 100g are taken, of which 67.01g of Pb3O4, 15.42g of ZrO2, 12.10g of TiO2, 0.61g of MnO2, 1.87g of Nb2O5, 2.11g of Bi2O3, 0.47g of ZnO, 0.30g of LiBiO2, and 0.10g of NiO are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 850°C, and the piezoelectric properties of the sintered disc are d33=323pC / N, the dielectric constant=1330, Kp=0.6, and tanδ=0.4%.

[0072] Comparative Example:

[0073] In this comparative example, 0.04Bi(Ni 1 / 2 Ti 1 / 2 )O3-0.06Pb(Mn 1 / 3 Nb 2 / 3 )O3-0.9Pb(Zr 0.5 Ti 0.5 )O3 ratio of each component weighed, the total weight of the above material is 100g, among which, 66.43g of Pb3O4, 16.79g of ZrO2, 11.37g of TiO2, 0.53g of MnO2, 1.61g of Nb2O5, 8.82g of Bi2O3, and 0.45g of ZnO are weighed, and the piezoelectric ceramic material is prepared according to the preparation method in Example 1. The sintering temperature is 1180℃, and the piezoelectric properties of the sintered disc are d33=355pC / N, the dielectric constant=1512, Kp=0.58, and tanδ=0.4%.

[0074] It can be seen from the above embodiments and comparative examples that the piezoelectric ceramic material provided in the present application has a lower sintering temperature and can ensure that the piezoelectric performance remains within a higher range and the loss remains within a lower range, thereby improving the performance stability of devices made of piezoelectric ceramic materials.

[0075] The above embodiments focus on the differences between the various embodiments. As long as the different optimization features between the various embodiments are not contradictory, they can be combined to form a better embodiment. Considering the simplicity of the text, they will not be repeated here.

[0076] Although some specific embodiments of the present application have been described in detail by way of example, it should be understood by those skilled in the art that the above examples are only for illustration, not for limiting the scope of the present application. It should be understood by those skilled in the art that the above embodiments may be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.

Claims

1. A piezoelectric ceramic material, characterized in that: The chemical formula is: <h2 style=";text-align:left;direction:ltr">0.03Bi(Zn<h2 style=";text-align:left;direction:ltr"> 1 / 2 <h2 style=";text-align:left;direction:ltr"> Ti<h2 style=";text-align:left;direction:ltr"> 1 / 2 <h2 style=";text-align:left;direction:ltr"> )O3-0.07Pb(Mn<h2 style=";text-align:left;direction:ltr"> 1 / 3 <h2 style=";text-align:left;direction:ltr"> Nb<h2 style=";text-align:left;direction:ltr"> 2 / 3 <h2 style=";text-align:left;direction:ltr"> )O3-0.9Pb(Zr<h2 style=";text-align:left;direction:ltr"> 0.46 <h2 style=";text-align:left;direction:ltr"> Ti<h2 style=";text-align:left;direction:ltr"> 0.54 <h2 style=";text-align:left;direction:ltr"> )O3; The piezoelectric ceramic material further includes 0-0.5wt% of a sintering aid, wherein the sintering aid is one or more of LiBiO2, Fe2O3, NiO and ZnO; The sintering temperature of the piezoelectric ceramic material is 850° C.-950° C., the electromechanical coupling coefficient Kp of the piezoelectric ceramic material is ≥0.6, the Curie temperature Tc is >330° C., and the dielectric loss tan δ is ≤0.5%.

2. The piezoelectric ceramic material according to claim 1, characterized in that: The LiBiO2 is synthesized from Li2CO3 and Bi2O3 by a solid phase method.

3. The piezoelectric ceramic material according to claim 1, characterized in that: in, The Pb source uses PbO or Pb3O4, the Zr source uses ZrO2, the Ti source uses TiO2, the Mn source uses MnO2, the Zn source uses ZnO, and the Nb source uses Nb2O5.

4. A method for preparing a piezoelectric ceramic material according to any one of claims 1 to 3, characterized in that: include: Weigh the raw materials according to the ratio of the chemical formula, add deionized water to the raw materials, and perform dispersion and grinding to obtain a uniformly mixed material I; After drying and sieving material I, pre-calcining at a certain pre-calcining temperature to obtain synthetic material II, the pre-calcining temperature is 750-850°C; The synthesized material II is ground and dispersed to obtain the piezoelectric ceramic material.

5. A piezoelectric device, characterized in that: The piezoelectric ceramic material is prepared using the piezoelectric ceramic material described in any one of claims 1 to 3.

Images