A high-entropy bio-piezoelectric ceramic and its preparation method

Abstract

The present invention belongs to the technical field of high entropy ceramic materials, and specifically relates to a high entropy bio-piezoelectric ceramic and a preparation method thereof. The structure of the high entropy bio-piezoelectric ceramic of the present invention is an ABO3 type perovskite structure; the present invention is based on Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn or Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 The high-entropy bio-piezoelectric ceramic prepared by the present invention has good piezoelectric properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-entropy ceramic materials, and in particular relates to a high-entropy bio-piezoelectric ceramic and a preparation method thereof. Background Art

[0002] Biopiezoelectric ceramics, which exhibit excellent osteogenic activity due to their piezoelectric effect, similar to that of natural bone tissue, have attracted significant attention from bone tissue engineering researchers. They represent a new class of bioactive materials, distinct from conductive materials. These materials can connect electrical signals to the proliferation and differentiation of osteoblasts in vivo, promoting bone repair and holding great promise for future development.

[0003] Traditional single-component piezoelectric ceramic systems have relatively low piezoelectric performance and are unable to meet the needs of society's development for high-performance new materials. Existing technologies are developing multi-component piezoelectric composite ceramic systems in the hope of obtaining high-performance biopiezoelectric ceramics. However, multi-component piezoelectric ceramics still suffer from low solid solubility, which affects the material's piezoelectric performance. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a high-entropy bio-piezoelectric ceramic and a preparation method thereof.

[0005] The first object of the present invention is to provide a high entropy bio-piezoelectric ceramic, the structure of the high entropy bio-piezoelectric ceramic of the present invention is an ABO3 type perovskite structure; 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn or Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.5 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0006] In the early stages of this research, the present invention utilized traditional methods for constructing piezoelectric ceramics, namely, preparing piezoelectric ceramics through component design to adjust their composition and structure. This involved numerous component experiments, resulting in a significant amount of experimental and analytical work. Furthermore, if all components were to be tested, current experimental methods and time constraints would be nearly impossible to achieve. The present invention utilizes a "morphotropic phase boundary construction" approach to reduce the experimental workload and improve piezoelectric performance, thereby preparing piezoelectric ceramics. However, the same challenges arise when the number of components in the system increases, necessitating new design approaches for the design of multi-component piezoelectric ceramics.

[0007] The present invention adopts the design concept and preparation strategy of high entropy alloy to prepare bio-piezoelectric ceramics, and increases the ability to form a single-phase solid solution by increasing the solid solubility limit between components, thereby obtaining a new multi-principal component single-phase solid solution ceramic material. The present invention selects the BNT system with excellent piezoelectric and ferroelectric properties to directly dope and modify to obtain high entropy piezoelectric ceramics. 0.5 Na 0.5 TiO3, abbreviated as BNT, is a perovskite-type relaxor ferroelectric.

[0008] The present invention uses BNT as a matrix, Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powders as raw materials, and dopes Zr and Sn or dopes Zr, Sn and Hf at the B position in an equal molar ratio, and obtains (Bi 0.5 Na 0.5 )(Zr 1 / 3Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0009] A second object of the present invention is to provide a method for preparing a high-entropy biopiezoelectric ceramic, comprising the following steps:

[0010] Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, according to the general formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25)Weigh the raw materials in the stoichiometric ratio of O3.

[0011] It should be noted that, based on the theory of the "tolerance factor" of doping, the present invention preferably uses Zr, Sn, and Hf elements with the same valence as "Ti" in BNT for "covalent doping." Furthermore, the chemical properties and ionic radius of the four elements Ti, Zr, Sn, and Hf are similar. Based on the principles of crystal chemistry and ionic radius matching, the three elements Zr, Ti, and Sn, or the four elements Zr, Ti, Sn, and Hf, can be doped into the B site of the BNT lattice in equal molar ratios. After doping, the four elements Zr, Ti, Sn, and Hf occupy the B site lattice in equal molar ratios, which induces lattice distortion relative to the original BNT matrix crystal structure. The high entropy effect corresponding to the multi-principal element ceramic promotes the formation of a solid solution, which is beneficial to improving the piezoelectric effect of the BNT ceramic. At the same time, the BNT lattice is activated by forming a solid solution, generating ion vacancies, promoting diffusion, and reducing the sintering temperature.

[0012] Step 2: wet ball milling the raw materials, and then drying and pre-calcining to obtain reaction powder.

[0013] The present invention wet-mills the raw materials to obtain a uniform raw material mixture and enhances the reactivity of the powder. The wet-milling medium is anhydrous ethanol. Drying and pre-calcining the milled raw materials facilitates the initial reaction of the raw materials, generates precursors, and enhances the subsequent sintering effect.

[0014] Preferably, the drying temperature is 30° C. to 80° C., and the drying time is 10 h to 12 h.

[0015] Preferably, the pre-firing temperature is 600° C. to 900° C., and the pre-firing time is 3 h to 5 h.

[0016] Step 3: ball-mill the reaction powder for a second time, dry it, add paraffin wax to granulate it, and press it into shape to obtain a ceramic green body.

[0017] Preferably, the conditions for the primary ball milling and the secondary ball milling are: the ball milling time is 2 hours to 24 hours, the rotation speed of the ball mill is 4000 rpm to 5000 rpm, and the ball milling medium is anhydrous ethanol.

[0018] Preferably, the diameter of the mold used for the compression molding is 11 mm to 12 mm, the pressure is 4 MPa to 5 MPa, and the holding time is 4 s to 5 s.

[0019] Preferably, the amount of the paraffin wax is 7% to 8% of the total mass of the reaction powder.

[0020] Step 4: Place the ceramic green body into a tubular furnace and calcine it at 1000° C. to 1200° C. to obtain high-entropy bio-piezoelectric ceramics.

[0021] The ceramic green body is calcined at high temperature in a tube furnace to promote the solid-phase reaction of the reaction powder and form a stable ceramic phase structure. High-temperature calcination can improve the density and mechanical properties of the ceramic material. Preferably, the temperature is increased from room temperature to 1000°C to 1200°C at a heating rate of 3°C / min to 4°C / min during the calcination process. The temperature is held in the tube furnace for 2 to 6 hours, followed by cooling to room temperature.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention uses Zr, Sn and Hf elements with the same valence as "Ti" in BNT for "same valence doping", and the chemical properties and ionic radius of the four elements Ti, Zr, Sn and Hf are similar. The three elements Zr, Ti and Sn or the four elements Zr, Ti, Sn and Hf can be doped into the B site of the BNT lattice in an equal molar ratio. Compared with the original BNT matrix crystal structure, the lattice distortion is caused by the equal molar ratio doping of the B site, and the high entropy effect corresponding to the multi-principal element ceramic promotes the formation of solid solution, which is beneficial to improve the piezoelectric effect of BNT ceramics; at the same time, the BNT lattice is activated by forming a solid solution, ion vacancies are generated, diffusion is promoted, and the sintering temperature is reduced. The (Bi prepared by the present invention 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 high entropy bio-piezoelectric ceramics have a piezoelectric constant of 75pC / N, (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 The piezoelectric constant of the )O3 high entropy bio-piezoelectric ceramic is 80pC / N. The high entropy bio-piezoelectric ceramic prepared by the present invention has good piezoelectric properties.

[0024] The preparation process of the invention is simple, does not require atmosphere sintering, and has the characteristics of short sintering time, low sintering temperature, simple process and high efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 (Bi 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3, (Bi prepared in Example 1 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 and (Bi prepared in Example 2 0.5Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Piezoelectric constant of O3 bio-piezoelectric ceramics. DETAILED DESCRIPTION

[0026] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below with reference to specific embodiments and drawings.

[0027] In the description of the present invention, unless otherwise specified, all reagents used are commercially available and all methods used are conventional techniques in the art.

[0028] Example 1

[0029] This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0030] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn are doped at the B position in an equal molar ratio to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 high entropy bio-piezoelectric ceramics.

[0031] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps:

[0032] Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2 and SnO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 1 / 3Sn 1 / 3 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0033] Step 2: Prepare reaction powder:

[0034] 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol, shake horizontally, and ball mill for 12 h at 4000 rpm to obtain a slurry.

[0035] 2.2) The slurry was dried in an oven at 70°C for 12 h, and then pre-calcined in a tube furnace at 850°C for 4.7 h to obtain a reaction powder.

[0036] Step 3: Prepare ceramic green body:

[0037] 3.1) Place the reaction powder in a nylon jar and add 40 mL of ethanol. Shake well and perform a secondary ball milling for 12 h at 4000 rpm.

[0038] 3.2) Dry the mixed reaction powder at 70°C for 12 h, then add paraffin wax to granulate the mixture to obtain a precursor powder; the mass of the paraffin wax is 8% of the mass of the reaction powder.

[0039] 3.3) Compact the precursor powder into a ceramic green body with a diameter of 11 mm under a uniaxial pressure of 5 MPa for 4 s.

[0040] Step 4: Place the ceramic green body in a tube furnace and heat the temperature from room temperature to 1050°C at a heating rate of 3°C / min for calcination. The holding time is 4 hours, and then cool to room temperature in the furnace to obtain a high entropy bio-piezoelectric ceramic, namely (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3.

[0041] Example 2

[0042] This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0043] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr, Sn and Hf are doped at the B position in equal molar ratios to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0044] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps:

[0045] Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0046] Step 2: Prepare reaction powder:

[0047] 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol, shake horizontally, and ball mill for 12 h at 4000 rpm to obtain a slurry.

[0048] 2.2) The slurry was dried in an oven at 80°C for 12 h, and then pre-calcined in a tube furnace at 850°C for 4.5 h to obtain a reaction powder.

[0049] Step 3: Prepare ceramic green body:

[0050] 3.1) Place the reaction powder in a nylon jar and add 40 mL of ethanol. Shake well and perform a secondary ball milling for 12 h at 4000 rpm.

[0051] 3.2) The mixed reaction powder is dried at 80°C for 12 h and granulated with paraffin wax to obtain a precursor powder; the mass of the paraffin wax is 9% of the mass of the reaction powder.

[0052] 3.3) Compact the precursor powder into a ceramic green body with a diameter of 12 mm under a uniaxial pressure of 4 MPa for 5 s.

[0053] Step 4: Place the ceramic green body in a tube furnace and heat the temperature from room temperature to 1050°C at a heating rate of 4°C / min for calcination. The holding time is 4 hours, and then the green body is cooled to room temperature to obtain a high entropy bio-piezoelectric ceramic, namely (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3.

[0054] Example 3

[0055] This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0056] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr, Sn and Hf are doped at the B position in equal molar ratios to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0057] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps:

[0058] Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0059] Step 2: Prepare reaction powder:

[0060] 2.1) Place the above raw materials in a nylon jar, add 40 mL of ethanol, shake horizontally, and ball mill for 2 h at 4000 rpm to obtain a slurry.

[0061] 2.2) The slurry was dried in an oven at 30°C for 10 h, and then pre-calcined in a tube furnace at 600°C for 3 h to obtain a reaction powder.

[0062] Step 3: Prepare ceramic green body:

[0063] 3.1) Place the reaction powder in a nylon jar and add 40 mL of ethanol. Shake well and perform a second ball milling for 10 h at 4000 rpm.

[0064] 3.2) The mixed reaction powder is dried at 30°C for 10 h and granulated with paraffin wax to obtain a precursor powder; the mass of the paraffin wax is 9% of the mass of the reaction powder.

[0065] 3.3) Compact the precursor powder into a ceramic green body with a diameter of 11 mm under a uniaxial pressure of 4 MPa for 4 s.

[0066] Step 4: Place the ceramic green body in a tubular furnace and heat the temperature from room temperature to 1000°C at a heating rate of 4°C / min for calcination. The holding time is 2 hours, and then the green body is cooled to room temperature in the furnace to obtain a high-entropy bio-piezoelectric ceramic.

[0067] Example 4

[0068] This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0069] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr, Sn and Hf are doped at the B position in equal molar ratios to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25)O3 high entropy bio-piezoelectric ceramics.

[0070] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps:

[0071] Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0072] Step 2: Prepare reaction powder:

[0073] 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol, shake horizontally, and ball mill for 2 h at 4000 rpm to obtain a slurry.

[0074] 2.2) The slurry was dried in an oven at 80°C for 12 h, and then pre-calcined in a tube furnace at 900°C for 5 h to obtain a reaction powder.

[0075] Step 3: Prepare ceramic green body:

[0076] 3.1) Place the reaction powder in a nylon jar and add 40 mL of ethanol. Shake well and perform a secondary ball milling for 24 h at 5000 rpm.

[0077] 3.2) The mixed reaction powders were dried at 80°C for 12 h, and then paraffin wax was added to granulate the mixture to obtain a precursor powder; wherein the mass of the paraffin wax was 9% of the mass of the reaction powders.

[0078] 3.3) Compact the precursor powder into a ceramic green body with a diameter of 12 mm under a uniaxial pressure of 5 MPa for 5 s.

[0079] Step 4: Place the ceramic green body in a tubular furnace and heat the temperature from room temperature to 1200°C at a heating rate of 4°C / min for calcination. The holding time is 6 hours, and then cool to room temperature in the furnace to obtain high-entropy bio-piezoelectric ceramics.

[0080] Comparative Example 1

[0081] This comparative example provides a medium-entropy bio-piezoelectric ceramic.

[0082] This comparative example uses Bi 0.5 Na 0.5 TiO3 is used as the matrix and Zr is doped at the B position in an equal molar ratio to obtain the chemical formula (Bi 0.5Na 0.5 )(Zr 0.5 Ti 0.5 )O3 medium-entropy bio-piezoelectric ceramics.

[0083] The medium entropy bio-piezoelectric ceramics of this comparative example are prepared by the following steps:

[0084] Step 1: Using Bi2O3, Na2CO3, TiO2 and ZrO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0085] Step 2: Prepare reaction powder:

[0086] 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol, shake horizontally, and ball mill for 12 h at 4000 rpm to obtain a slurry.

[0087] 2.2) The slurry was dried in an oven at 70°C for 12 h, and then pre-calcined in a tube furnace at 850°C for 4.7 h to obtain a reaction powder.

[0088] Step 3: Prepare ceramic green body:

[0089] 3.1) Place the reaction powder in a nylon jar and add 40 mL of ethanol. Shake well and perform a secondary ball milling for 12 h at 4000 rpm.

[0090] 3.2) Dry the mixed reaction powder at 70°C for 10 h, then add paraffin wax to granulate the mixture to obtain a precursor powder; the mass of the paraffin wax is 9% of the mass of the reaction powder.

[0091] 3.3) The precursor powder was pressed into a ceramic green body with a diameter of 11 mm under a uniaxial pressure of 4 MPa.

[0092] Step 4: Place the ceramic green body in a tube furnace and heat the temperature from room temperature to 1050°C at a heating rate of 3°C / min for calcination. The holding time is 4 hours, and then the green body is cooled to room temperature to obtain a medium entropy bio-piezoelectric ceramic, namely (Bi 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3.

[0093] Experimental test:

[0094] 1. Mixed entropy

[0095] The present invention calculates the mixing entropy values ​​of the bio-piezoelectric ceramics prepared in Example 1, Example 2 and Comparative Example 1 according to the mixing entropy value formula, and the mixing entropy values ​​are shown in Table 1.

[0096] Mixing entropy S config =-R[ ], where x a 、x b and x c They refer to the mole fractions of A-site, B-site and C-site ions respectively, A-site refers to the A site, B-site refers to the B site, and C-site refers to the C site.

[0097] Table 1 Mixing entropy values ​​of biopiezoelectric ceramics prepared in Example 1, Example 2 and Comparative Example 1

[0098]

[0099] It can be seen from Table 1 that with the increase of doping elements, the doping elements are doped into the B site of the BNT lattice in equal molar ratios, and the multi-principal element ceramics formed increase the high entropy effect.

[0100] 2. Piezoelectric test

[0101] Using the GB / T3389 2008 test standard, the ceramic samples prepared in Examples 1 to 2 and Comparative Example 1 were polished, cleaned, and dried, and the upper and lower ends of the ceramic samples were silvered and dried to obtain polarized ceramic samples. The upper and lower surfaces of the polarized ceramic samples were placed between two electrodes on the test bench, and the distance between the two electrodes was adjusted until the ceramic sample and the stage fixture did not vibrate, and data was read. The piezoelectric constant test was performed using a SA1303A quasi-static d 33 Measuring instrument, the test temperature is room temperature. Piezoelectric constant d 33 The results are as follows Figure 1 shown.

[0102] Figure 1 (Bi prepared in Comparative Example 1 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3, (Bi prepared in Example 1 0.5 Na 0.5 )(Zr 1 / 3Ti 1 / 3 Sn 1 / 3 )O3 and (Bi prepared in Example 2 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25)Piezoelectric constant of O3 bio-piezoelectric ceramics. Figure 1 It can be seen that the piezoelectric constants of the high-entropy bio-piezoelectric ceramics prepared in Comparative Example 1, Example 1, and Example 2 are 60pC / N, 80pC / N, and 75pC / N, respectively. Compared with Comparative Example 1, the piezoelectric properties of the high-entropy bio-piezoelectric ceramics prepared in Examples 1 and 2 are improved. This is because the doped elements occupy the B-site lattice in equal molar ratios, causing lattice distortion. At the same time, the high-entropy effect corresponding to the multi-principal element ceramics promotes the formation of solid solution; the high-entropy effect and the lattice distortion effect synergistically promote the improvement of the piezoelectric properties of BNT ceramics; and the piezoelectric constant of the high-entropy bio-piezoelectric ceramics prepared in Example 2 is slightly lower than that of the high-entropy bio-piezoelectric ceramics prepared in Example 1, which may be due to the slightly excessive element doping that destroys the ceramic solid solubility and the final crystal structure to a certain extent.

[0103] XRD test shows that the (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high-entropy bio-piezoelectric ceramics have similar characteristic peaks, indicating that they have the same phase structure and similar piezoelectric properties.

[0104] It should be noted that when numerical ranges are mentioned in the present invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints may be selected. Since the steps and methods used are the same as those in the embodiments, the present invention describes preferred embodiments to avoid redundancy. Although preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they understand the basic inventive concepts, and such changes and modifications fall within the scope of the present invention.

[0105] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. If these modifications and variations of the present invention fall within the scope of the equivalent technology of the present invention, the present invention is also intended to include these modifications and variations.

Claims

1. A high-entropy biopiezoelectric ceramic, characterized in that: The structure of the high entropy bio-piezoelectric ceramic is an ABO3 type perovskite structure; Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn or Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics; The preparation method of the high entropy bio-piezoelectric ceramic is as follows: With Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, according to the general formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 ) Weigh the raw materials in the stoichiometric ratio of O3; The raw materials are wet ball-milled and mixed, and then dried and pre-calcined to obtain reaction powder; The reaction powder is ball-milled for a second time, dried, and granulated by adding paraffin wax, and then pressed into shape to obtain a ceramic green body; The ceramic green body is placed in a tube furnace and calcined at 1000°C to 1200°C to obtain high-entropy bio-piezoelectric ceramics.

2. A method for preparing the high-entropy biopiezoelectric ceramic according to claim 1, characterized in that: The following steps are involved: With Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, according to the general formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 ) Weigh the raw materials in the stoichiometric ratio of O3; The raw materials are wet ball-milled and mixed, and then dried and pre-calcined to obtain reaction powder; The reaction powder is ball-milled for a second time, dried, and granulated by adding paraffin wax, and then pressed into shape to obtain a ceramic green body; The ceramic green body is placed in a tube furnace and calcined at 1000°C to 1200°C to obtain high-entropy bio-piezoelectric ceramics.

3. The method for preparing the high-entropy biopiezoelectric ceramic according to claim 2, wherein: During the calcination process, the temperature is raised from room temperature to 1000° C. to 1200° C. at a heating rate of 3° C. / min to 4° C. / min, kept at this temperature for 2 h to 6 h, and then cooled to room temperature along with the furnace.

4. The method for preparing a high-entropy biopiezoelectric ceramic according to claim 2, wherein: The pre-firing temperature is 600° C. to 900° C., and the pre-firing time is 3 h to 5 h.

5. The method for preparing high-entropy biopiezoelectric ceramics according to claim 2, characterized in that: The pressing pressure is 4 MPa to 5 MPa, and the holding time is 3 s to 4 s.

6. The method for preparing high-entropy bio-piezoelectric ceramics according to claim 2, characterized in that: The conditions for the primary ball milling and the secondary ball milling are as follows: the ball milling time is 2 hours to 24 hours, the rotation speed of the ball mill is 4000 rpm to 5000 rpm, and the ball milling medium is anhydrous ethanol.

7. The method for preparing high-entropy bio-piezoelectric ceramics according to claim 2, characterized in that: The mass of the paraffin wax is 7% to 8% of the total mass of the reaction powder.

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