A photopolymerizable piezoelectric ceramic with ultra-high energy harvesting performance, its preparation method and application

Abstract

This invention discloses a photopolymerizable piezoelectric ceramic with ultra-high energy harvesting performance, its preparation method, and its applications, relating to the field of piezoelectric ceramic technology. The method includes adding PIN-PMN-PZ-PT nanoparticles to a surface modification solution, followed by ball milling to obtain surface-functionalized PIN-PMN-PZ-PT nanoparticles; designing a three-dimensional structural model with a complex three-dimensional periodic structure; feeding the PIN-PMN-PZ-PT-based piezoelectric ceramic slurry into the feed tank of a photopolymerizer, importing the three-dimensional structural model into the photopolymerizer, setting printing parameters, and printing to obtain a green body; and debinding and sintering the green body to obtain the piezoelectric ceramic. This invention, by combining different photopolymerizable monomer resins, produces single-layer sheets with high strength and good toughness, and optimizes the optimal photoinitiator and its dosage. It achieves lightweight preparation of piezoelectric ceramics, offering significant advantages in the field of energy harvesting and possessing significant application and theoretical value.

Description

Technical Field

[0001] This invention relates to the field of piezoelectric ceramics technology, specifically to a multi-component piezoelectric ceramic with ultra-high energy harvesting performance that can be photocured, its preparation method, and its application. Background Technology

[0002] Piezoelectric sensors, based on the principle of electromechanical energy conversion, primarily measure force, as well as other quantities such as pressure, acceleration, temperature, and strain, by converting acquired data into electrical charges. Piezoelectric sensors are widely used for vibration and shock measurements. They have applications in various fields, including medical, aerospace, consumer electronics, and nuclear instruments. Currently, the most widely used and mature piezoelectric ceramic devices are based on perovskite-type lead zirconate titanate (Pb(Zr)). x Ti 1-x Lead zirconate titanate (Pb(Zr)) is a type of ceramic material based on lead zirconate titanate (Pb(Zr)). 1-x TiO3 and PZT ceramics possess excellent piezoelectric and dielectric properties. Due to their good stability, high precision, high energy conversion efficiency, fast response speed, mechanical quality factor, piezoelectric coefficient, and electromechanical coupling constant are significantly superior to lead-free piezoelectric ceramics.

[0003] Due to the high hardness, high strength, and brittleness of ceramics, manufacturing piezoelectric ceramic parts with complex structures is quite challenging. Furthermore, the mechanical stress generated by traditional processing methods can lead to depolarization of piezoelectric ceramic parts, thereby reducing their piezoelectric properties. Technologies combining forming and processing have become a research hotspot. Compared to traditional processing methods, additive manufacturing technology can achieve integrated forming and processing of complex-designed piezoelectric ceramic parts. These technologies can meet the requirements of modern engineering applications. Among various additive manufacturing technologies, photopolymer 3D printing technology has advantages such as high production precision, fast forming speed, and good surface quality.

[0004] The performance of traditional piezoelectric materials depends on their crystal structure. The crystal structure determines the piezoelectric properties of piezoelectric ceramics. Once the piezoelectric material used is determined, its crystal structure or molecular structure determines the magnitude of its piezoelectric constant and the form of its piezoelectric constant matrix. Its directionality is determined, and each coefficient is also determined. Changing the crystal structure or molecular structure of a piezoelectric material requires a lot of manpower and resources. However, by using 3D printing technology to develop piezoelectric ceramic metamaterials through microstructure design, the ratio or magnitude of the piezoelectric coefficients in any direction can be controlled.

[0005] For Pb(Mg) 1 / 3 Nb 2 / 3 O3-Pb(In) 1 / 2 Nb 1 / 2Piezoelectric ceramics (Pb-PbZrO3-PbTiO3, PIN-PMN-PZ-PT) exhibit strong light absorption in the ultraviolet wavelength range. During the photopolymerization printing process, ultraviolet light has difficulty penetrating the powder in the paste to reach deeper layers. Typically, nanoparticles (particle size d...) are used... 50 Piezoelectric ceramic slurries (at the 100-nanometer level) possess large specific surface areas and high surface activity, resulting in good electrical properties when sintered into ceramics. However, the layer-by-layer obstruction and light absorption of nanoparticles in the photocuring slurry make it difficult to form an effective network cross-linking structure of the monomer resin. The curing depth is not only less than 20 μm, but the mechanical properties of the cured single-layer sheet are also very poor. Consequently, piezoelectric ceramic slurries prepared using PIN-PMN-PZ-PT nanoparticles are not suitable for many common photocuring 3D printing equipment on the market. At the same time, when the solid content (volume fraction) of PIN-PMN-PZ-PT nanoparticles in the slurry increases to about 40 vol%, the viscosity of the slurry increases sharply, making it difficult for the squeegee to spread the slurry during printing, resulting in poor slurry flowability. In addition, the density of PIN-PMN-PZ-PT nanoparticles is about 7 times that of the monomer resin, making them prone to sedimentation during photocuring printing. This leads to different contents of PIN-PMN-PZ-PT nanoparticles in the upper and lower parts of the cured green body, resulting in different shrinkage rates in the Z direction. This causes problems such as deformation, warping, and even cracking during subsequent debinding and sintering. Some samples with complex three-dimensional structures are difficult to mold, failing to leverage the advantages of photopolymerization printing. Currently, there is limited research on photopolymerization molding processes for multi-component piezoelectric ceramics, and research on the relevant performance of printing complex structures is almost non-existent. Furthermore, no research has explored the potential of photopolymerized piezoelectric ceramics in the field of energy harvesting.

[0006] Existing techniques for preparing PIN-PMN-PZ-PT-based piezoelectric ceramic slurries with poor curing capabilities typically involve pre-firing the original powder at temperatures above 700 degrees Celsius for more than 1 hour. This transforms the fine powder with micro-nano particle sizes into coarse powder, significantly reducing the curing challenges caused by light scattering. However, this process incurs additional costs due to pre-firing, and some lead content in the powder also volatilizes during the pre-firing process. Furthermore, the kinetic energy for debinding and sintering of PZT-based piezoelectric ceramics prepared by printing with coarse powder is far less than the sintering energy provided by the high surface energy and high fluidity of nanoparticles. Consequently, the resulting samples do not perform as well as those printed directly from the original nanoparticles, exhibiting poorer piezoelectric properties. In addition, the pre-firing process is not ideal for preparing large batches of samples, as the preparation of large quantities of slurry requires a large amount of powder, and the sintering of such large quantities of powder requires numerous crucibles and sintering furnaces, further increasing costs and time. Summary of the Invention

[0007] To address the shortcomings of the aforementioned background technology, this invention provides for PIN-PMN-PZ-PT based piezoelectric ceramics. The nanopowders, due to their better flowability and high surface energy during sintering, exhibit a denser structure and superior piezoelectric properties compared to micron-sized powders. When the particle size d... 50 At the micro-nano scale (<500nm), the smaller the particle size, the shallower the curing depth. Furthermore, the high specific surface area makes the powder prone to agglomeration. Currently, the common solution is to obtain coarse powder through pre-firing, achieving better curing depth and dispersibility at larger particle sizes. However, this method undoubtedly increases capital and time costs. Simultaneously, coarse powder has lower kinetic energy during debinding and sintering compared to nanoparticles, resulting in more defects such as pores and cracks, deteriorating piezoelectric properties. Moreover, the additional lead volatilization during pre-firing also worsens the performance of PIN-PMN-PZ-PT based piezoelectric ceramics. To address the numerous problems existing in the direct printing of PIN-PMN-PZ-PT nanoparticles, it is necessary to fill the gaps in ultrafine nanoparticle (d... 50 There is a gap in understanding the excellent photocuring performance (including curing depth, viscosity, sedimentation stability, dispersion stability, and solid content) of piezoelectric ceramics with a wavelength of <200nm. Current research on the influence of macro- and micro-structures on the intrinsic electromagnetic parameters of multi-component piezoelectric ceramics is extremely rare. Complex structures formed by photocuring 3D printing typically exhibit poor performance and are difficult to study systematically. This invention provides a photocurable multi-component piezoelectric ceramic with ultra-high energy harvesting performance, its preparation method, and its applications. This method involves surface modification of PIN-PMN-PZ-PT nanoparticles, adding substances with ultra-low refractive index differences to the resin, selecting suitable dispersants and appropriate amounts of photoinitiators, thereby eliminating the need for a pre-firing process and directly completing the photocuring printing of PIN-PMN-PZ-PT nanoparticles, reducing both financial and time costs.

[0008] The first objective of this invention is to provide a method for preparing a multi-component piezoelectric ceramic with ultra-high energy harvesting performance through photopolymerization, comprising the following steps:

[0009] Preparation of PIN-PMN-PZ-PT nanoparticles;

[0010] PIN-PMN-PZ-PT nanoparticles were added to a surface modification solution and ball-milled to obtain surface-functionalized PIN-PMN-PZ-PT nanoparticles.

[0011] The photocurable monomer resin, soluble starch, dispersant, reactive diluent, and defoamer are mixed evenly to obtain a photosensitive resin organic polymer system.

[0012] Surface-functionalized PIN-PMN-PZ-PT nanoparticles were added in batches to a photosensitive resin organic polymer system, ball-milled, and then a photoinitiator was added for further ball milling to obtain a PIN-PMN-PZ-PT-based piezoelectric ceramic slurry.

[0013] Design three three-dimensional structural models with complex three-dimensional periodic structures;

[0014] The PIN-PMN-PZ-PT based piezoelectric ceramic slurry is put into the material tank of the photopolymer printer, and the three-dimensional structural model is imported into the photopolymer printer. The printing parameters are set, and the green body is printed.

[0015] After degreasing and sintering the blank, piezoelectric ceramics are obtained.

[0016] Preferably, the surface modification solution is prepared by dissolving a silane coupling agent in ethanol;

[0017] The silane coupling agent is γ-glycidoxypropyltrimethoxysilane or γ-methacryloxypropyltrimethoxysilane;

[0018] The mass fraction of silane coupling agent in the surface modification solution is 4-6%.

[0019] Preferably, the amount of the surface modification solution added accounts for 1 to 5 wt% of the mass of the PIN-PMN-PZ-PT nanoparticles.

[0020] Preferably, the photocurable monomer resin is one or more selected from 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, and epoxy acrylate; the amount of the photocurable monomer resin added accounts for 10-15 wt% of the photocurable slurry.

[0021] The dispersant is one or more of DISPERBYK-110, DISPERBYK-142, and DISPERBYK-111; the amount of the dispersant added is 1-3 wt% of the UV-curable slurry.

[0022] The reactive diluent is Triton X-100; the amount of the reactive diluent added is 0.5~1wt% of the photocurable slurry.

[0023] The defoamer is Z-2006 ceramic slurry defoamer; the amount of defoamer added is 0.1~0.3 wt% of the UV-cured slurry.

[0024] The amount of soluble starch added accounts for 10~20 vol% of the volume fraction of PIN-PMN-PZ-PT nanoparticles.

[0025] Preferably, the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; the amount of photoinitiator added accounts for 5 to 20 wt% of the resin.

[0026] Preferably, the PIN-PMN-PZ-PT nanoparticle content in the PIN-PMN-PZ-PT based piezoelectric ceramic slurry is 80~85wt%; the particle size d of the PIN-PMN-PZ-PT nanoparticles is... 50 <200nm.

[0027] Preferably, the printing parameters are: single-layer thickness 15~30μm, exposure current 2000~5000mA, exposure time 5~15s per layer, and squeegee speed 800step / s.

[0028] Preferably, the degreasing process includes: under an inert atmosphere, heating from room temperature to 300°C for 300 minutes, holding at 300°C for 60 minutes, then heating to 400°C for 400 minutes, holding at 400°C for 60 minutes, then heating to 450°C for 200 minutes, holding at 400°C for 60 minutes, then heating to 500°C for 250 minutes, holding at 500°C for 60 minutes, then heating to 550°C for 250 minutes, holding at 550°C for 60 minutes, then heating to 600°C for 250 minutes, holding at 60 minutes, and then cooling in the furnace to remove O and H elements;

[0029] The sintering process includes: heating to 300°C in air at room temperature for 300 minutes, holding at 300°C for 60 minutes, then heating to 450°C for 150 minutes, holding at 450°C for 120 minutes, then heating to 600°C for 150 minutes, holding at 600°C for 120 minutes, then heating to 1300°C for 350 minutes, holding at 1300°C for 120 minutes, and then cooling with the furnace.

[0030] The second objective of this invention is to provide a multi-component piezoelectric ceramic with ultra-high energy harvesting performance that can be photocured.

[0031] The third objective of this invention is to provide an application of a multi-component piezoelectric ceramic with ultra-high energy harvesting performance through photopolymerization in the field of energy harvesting.

[0032] Compared with the prior art, the beneficial effects of the present invention are:

[0033] This invention provides a multi-component piezoelectric ceramic with ultra-high energy harvesting performance that can be photocured, along with its preparation method and applications. By screening the type and amount of dispersant, this invention maintains a suitable printing viscosity (<3 Pa·s) and good flowability at a high solids content (40 vol%). By surface functionalizing PIN-PMN-PZ-PT nanoparticles, the rheological properties of the slurry are further improved, and the sedimentation problem is basically solved. The stability of the slurry can still reach more than 95% after standing for 48 hours. By selecting the type and optimal amount of photoinitiator, the single-layer curing depth can reach more than 50 μm, solving the problem of poor curing ability of slurries prepared from PIN-PMN-PZ-PT nanoparticles. At the same time, the cured part has good surface quality and low surface roughness.

[0034] This invention enables the fabrication of complex three-dimensional periodic structures (chiral torsional sandwich structures, body-centered cubic sandwich structures, and straight-bar array sandwich structures). The feature size of the smallest structure is less than 200 μm, and the piezoelectric constant exceeds 500 pC / N, achieving over 97% of the accuracy of dry pressing. Furthermore, the fabricated three-dimensional periodic complex structures exhibit high structural fidelity, with the designed solid component accounting for only 20% of the total mass, meaning only 20% of the mass of a square solid sample of the same size. Due to its porous nature, the metamaterial can be considered a composite material of PIN-PMN-PZ-PT piezoelectric ceramic and air. In the system of a high-dielectric-constant PIN-PMN-PZ-PT matrix and a low-dielectric-constant air, the reduced solid component increases the air component, significantly lowering the dielectric constant and increasing its energy harvesting factor d. 33 ×g 33 Exceeding 65000×10 -15 m 2 / N has a significant advantage in the field of energy harvesting.

[0035] This invention directly selects particle size d 50PIN-PMN-PZ-PT nanoparticles (<200nm) do not require pre-calcination into coarse powder before slurry preparation. This invention utilizes a silane coupling agent to surface-functionalize the PIN-PMN-PZ-PT piezoelectric nanoparticles, solving the sedimentation problem and enhancing the piezoelectric response. This invention optimizes different dispersants and their dosages to achieve suitable printing viscosity. By combining different photocurable monomer resins, this invention produces single-layer sheets with high strength and good toughness, optimizing the optimal photoinitiator and its dosage. This invention adds soluble starch with an ultra-low refractive index difference to the photosensitive resin, significantly increasing the curing depth. This invention optimizes the debinding and sintering process using the thermogravimetric-differential thermal curves of the photocured preform, resulting in sintered samples with fewer defects and less deformation. This invention designs three piezoelectric structures suitable for photocurable 3D printing. The prepared samples exhibit excellent piezoelectric and energy harvesting properties. The structural design concept of adding two thin plates above and below the superstructure is highly suitable for the photocurable design of piezoelectric ceramics, and the design approach is applicable to the 3D printing process of various piezoelectric ceramic metamaterials. Attached Figure Description

[0036] Figure 1 This is a flowchart of the photopolymerization printing process for PIN-PMN-PZ-PT-based piezoelectric ceramics provided by the present invention;

[0037] Figure 2 This is a schematic diagram of PIN-PMN-PZ-PT nanoparticles modified with silane coupling agent;

[0038] Figure 3 The sedimentation experiment was conducted on the photocurable slurry prepared before and after nanoparticle surface modification.

[0039] Figure 4 The settling rate curves are of the photocurable slurry prepared before and after nanoparticle surface modification;

[0040] Figure 5 Model diagrams of superstructured unit cells: (a) chiral torsion structure; (b) body-centered cubic structure;

[0041] Figure 6 These are structural morphology images under a scanning electron microscope: (a) chiral torsion sandwich structure; (b) body-centered cubic structure; (c) straight bar array sandwich structure;

[0042] Figure 7 The present invention describes the electrical properties of three three-dimensional periodic complex structures. Detailed Implementation

[0043] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0044] This invention designs a piezoelectric structure suitable for photopolymerization 3D printing. The structural design not only retains the main macroscopic structure to maximize the direct influence between the piezoelectric response and the macroscopic structure, but also uses two thin plates above and below the periodic structure to simplify the subsequent silvering polarization operation. This enables the fabrication of complex three-dimensional periodic structures, allowing for the systematic study of the influence of macroscopic structure on electrical properties while maintaining good original performance. Simultaneously, it achieves the fabrication of high-performance, lightweight, and complex three-dimensional periodic multi-component piezoelectric ceramics.

[0045] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a multi-component piezoelectric ceramic with ultra-high energy harvesting performance by photopolymerization, comprising the following steps:

[0046] Preparation of PIN-PMN-PZ-PT nanoparticles;

[0047] PIN-PMN-PZ-PT nanoparticles were added to a surface modification solution and ball-milled to obtain surface-functionalized PIN-PMN-PZ-PT nanoparticles.

[0048] The photocurable monomer resin, soluble starch, dispersant, reactive diluent, and defoamer are mixed evenly to obtain a photosensitive resin organic polymer system.

[0049] Surface-functionalized PIN-PMN-PZ-PT nanoparticles were added in batches to a photosensitive resin organic polymer system, ball-milled, and then a photoinitiator was added for further ball milling to obtain a PIN-PMN-PZ-PT-based piezoelectric ceramic slurry.

[0050] Design a three-dimensional structural model of a complex three-dimensional periodic structure;

[0051] The PIN-PMN-PZ-PT based piezoelectric ceramic slurry is put into the material tank of the photopolymer printer, and the three-dimensional structural model is imported into the photopolymer printer. The printing parameters are set, and the green body is printed.

[0052] After degreasing and sintering the blank, piezoelectric ceramics are obtained.

[0053] The mechanism of action of PIN-PMN-PZ-PT nanoparticles modified by silane coupling agents in this invention is shown in Figure 2. The Si-OH generated from the hydrolysis of the silicon-oxygen covalent bonds in KH570 condenses with the hydroxyl-OH groups on the surface of the PIN-PMN-PZ-PT nanoparticles, chemically bonding them to the surface and leaving free methacrylate on the surface. The aforementioned gradient concentration setting optimizes the surface functionalization reaction, maximizing surface coverage. These strong covalent bonds between the piezoelectric nanoparticles and the photocurable monomer resin network improve the dispersion quality of the high-concentration piezoelectric paste by creating a spatially hindered surface. This general-purpose process is not limited to PIN-PMN-PZ-PT. Surface functionalization can enhance the piezoelectric response of various piezoelectric materials (e.g., barium titanate BTO) or other functional materials (e.g., bismuth multiferrite). Existing technologies mainly achieve good stability and low viscosity simultaneously through dispersants. However, this dual-functionality of dispersants means that while viscosity is reduced, stability cannot be well guaranteed, as high viscosity is beneficial for anti-settling. This invention allows the silane coupling agent and dispersant to perform their respective functions, maintaining suitable viscosity while possessing excellent anti-settling properties. The sedimentation experiments and results are as follows: Figure 3 and Figure 4 As shown, the two slurries used in the sedimentation experiment were prepared without modification by the silane coupling agent and provided in Example 1. The addition of soluble starch with an ultra-low refractive index difference to the photocurable monomer resin was to improve the curing ability of the multi-component piezoelectric ceramic slurry. The addition of reactive diluent and defoamer further improved the rheological properties of the slurry and eliminated air bubbles in the slurry.

[0054] The surface modification solution is prepared by dissolving a silane coupling agent in ethanol.

[0055] The silane coupling agent is γ-glycidoxypropyltrimethoxysilane or γ-methacryloxypropyltrimethoxysilane;

[0056] The mass fraction of silane coupling agent in the surface modification solution is 4-6%.

[0057] The amount of the surface modification solution added is 1 to 5 wt% of the mass of PIN-PMN-PZ-PT nanoparticles.

[0058] The photocurable monomer resin is one or more selected from 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, and epoxy acrylate; the amount of the photocurable monomer resin added accounts for 10-15 wt% of the photocurable slurry.

[0059] The dispersant is one or more of DISPERBYK-110, DISPERBYK-142, and DISPERBYK-111; the amount of the dispersant added is 1-3 wt% of the UV-curable slurry.

[0060] The reactive diluent is Triton X-100; the amount of the reactive diluent added is 0.5~1wt% of the photocurable slurry.

[0061] The defoamer is Z-2006 ceramic slurry defoamer; the amount of defoamer added is 0.1~0.3 wt% of the UV-cured slurry.

[0062] The amount of soluble starch added accounts for 10~20 vol% of the volume fraction of PIN-PMN-PZ-PT nanoparticles.

[0063] The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; the amount of the photoinitiator added accounts for 5-20 wt% of the resin.

[0064] The PIN-PMN-PZ-PT nanoparticle content in the PIN-PMN-PZ-PT based piezoelectric ceramic slurry is 80~85wt%; the particle size d of the PIN-PMN-PZ-PT nanoparticles is... 50 <200nm.

[0065] The printing parameters are: single layer thickness 15~30μm, exposure current 2000~5000mA, exposure time 5~15s per layer, and squeegee speed 800step / s.

[0066] The degreasing process includes: under an inert atmosphere, heating from room temperature to 300°C for 300 minutes, holding at 300°C for 60 minutes, then heating to 400°C for 400 minutes, holding at 300°C for 60 minutes, then heating to 450°C for 200 minutes, holding at 450°C for 60 minutes, then heating to 500°C for 250 minutes, holding at 500°C for 60 minutes, then heating to 550°C for 250 minutes, holding at 550°C for 60 minutes, then heating to 600°C for 250 minutes, holding at 60 minutes, and then cooling in the furnace to remove O and H elements;

[0067] The sintering process includes: heating to 300°C in air at room temperature for 300 minutes, holding at 300°C for 60 minutes, then heating to 450°C for 150 minutes, holding at 450°C for 120 minutes, then heating to 600°C for 150 minutes, holding at 600°C for 120 minutes, then heating to 1300°C for 350 minutes, holding at 1300°C for 120 minutes, and then cooling with the furnace.

[0068] In one embodiment, a method for preparing a multi-component piezoelectric ceramic with ultra-high energy harvesting performance by photopolymerization is provided, see [link to previous document]. Figure 1 As shown, it specifically includes the following:

[0069] Step 1: Weigh out a quantity of PIN-PMN-PZ-PT nanoparticles.

[0070] The particle size d of the PIN-PMN-PZ-PT nanoparticles described in step 1 50 <200nm, the amount added accounts for 80~85wt% of the final photocurable slurry.

[0071] The preparation method of PIN-PMN-PZ-PT nanoparticles includes:

[0072] PIN-PMN-PZ-PT nanoparticles were prepared using analytically pure MnO, Nb2O5, In2O3, PbO, ZrO2, and TiO2 as raw materials via a traditional solid-state method. First, MnNb2O6 and InNbO4 precursors were prepared by calcining MnO, Nb2O5, and In2O3 at 1100 ℃ and 1150 ℃ for 6 h, respectively. The prepared MnNb2O6 and InNbO4 were then mixed with PbO, ZrO2, and TiO2 in stoichiometric ratios, ball-milled in ethanol for 24 h, dried, and calcined at 800 ℃ for 3 h, followed by a second ball milling for 24 h. Finally, the nanoparticles were obtained by crushing, grinding, and sieving.

[0073] Step 2: Dissolve a certain mass fraction of surface functionalizing agent in anhydrous ethanol to prepare a modified solution of a certain concentration. Add the PIN-PMN-PZ-PT nanoparticles weighed in Step 1 to the modified solution, and then ball mill, dry, and sieve to obtain surface-functionalized PIN-PMN-PZ-PT nanoparticles.

[0074] The surface functionalizing agent is a silane coupling agent γ-glycidoxypropyltrimethoxysilane (KH560) or γ-methacryloyloxypropyltrimethoxysilane (KH570), and the amount added accounts for 1~5 wt% of the mass of PIN-PMN-PZ-PT nanoparticles. The mass fraction of the silane coupling agent in the solution prepared by dissolving it in ethanol is 5%.

[0075] During ball milling, the added grinding balls are zirconia grinding balls, with a mass ratio of 1:3 to 6 of the total mass of the added substances. The ball milling equipment used is a planetary ball mill, the ball milling time is between 6 and 12 hours, the ball milling speed is 300 to 500 r / min, and the drying after ball milling is done by evaporation of anhydrous ethanol. The drying temperature is 70 to 80℃, the drying time is 12 to 24 hours, and the sieve mesh is 500 mesh.

[0076] Step 3: Ball mill and mix the photocurable monomer resin, the substance with an ultra-low refractive index difference from the resin, the dispersant, the reactive diluent, and the defoamer until uniform to obtain the photosensitive resin organic polymer system.

[0077] The monomer resin is one or more of 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), polyethylene glycol diacrylate (PEGDA), and epoxy acrylate (EA), and the amount added accounts for 10-15 wt% of the photocurable slurry;

[0078] The substance with an ultra-low refractive index difference with the resin is soluble starch, and its addition amount accounts for 10~20 vol% of the volume fraction of PIN-PMN-PZ-PT nanoparticles.

[0079] The dispersant is one or more of DISPERBYK-110, DISPERBYK-142, and DISPERBYK-111 (Germany BYK dispersant), and the amount added is 1-3 wt% of the UV-cured slurry;

[0080] The reactive diluent is Triton X-100, and its addition amount is 0.5~1wt% of the UV-curable slurry;

[0081] The defoamer is Z-2006 ceramic slurry defoamer, and the amount added accounts for 0.1~0.3wt% of the UV-cured slurry.

[0082] Step 4: Add the surface-functionalized PIN-PMN-PZ-PT nanoparticles obtained in Step 2 to the photosensitive resin organic polymer system of Step 3 in batches and ball mill. Finally, add the photoinitiator and ball mill for a certain time to obtain a PIN-PMN-PZ-PT based piezoelectric ceramic slurry with high solid content, suitable viscosity, good stability, no agglomeration, and high curing depth.

[0083] Among them, there were 4 batches of modified PIN-PMN-PZ-PT nanoparticles. The photoinitiator was one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819). The amount added accounted for 5~20wt% of the resin. The grinding beads were zirconia grinding beads. The mass ratio of the added grinding beads to the photocurable slurry was between 1:3 and 1:6. The grinding time was 6~12h, the grinding speed was 300~500r / min, and the grinding equipment was a planetary ball mill.

[0084] Step 5: First, use SolidWorks software to draw the unit cell of the chiral torsion sandwich structure, body-centered cubic sandwich structure, or straight rod array sandwich structure, and adjust the feature size so that the height of the entire unit cell is 1.5mm. Then, array it between two rectangular thin plates with dimensions of 10mm×10mm×0.25mm. The thin plates are for subsequent silver coating and polarization operations, and finally obtain three piezoelectric ceramic metamaterial structures.

[0085] Step 6: Import the photocurable slurry obtained in step 4 into the material tank of the photocurable printer, import the periodic three-dimensional complex structure model, select appropriate printing parameters, and the printed blank is degreased and sintered to become ceramic.

[0086] The imported model is a chiral torsion sandwich structure, and the printing parameters are: single layer thickness 15~30μm, exposure current 2000~5000mA, exposure time 5~15s per layer, and squeegee speed 800step / s.

[0087] Degreasing is carried out under an inert atmosphere, with the temperature slowly increased between 300 and 600°C to remove the O and H elements from the photocurable organic polymer system. Sintering is carried out in air, with the temperature slowly increased between 300 and 600°C to remove the C element from the organic matter. The ceramic is then formed by holding the temperature at 1200 to 1400°C for 1 to 4 hours.

[0088] Step 7: The piezoelectric ceramic obtained in Step 6 is subjected to electrode polarization treatment, and its dielectric and piezoelectric properties are tested. The electrode polarization method is screen printing, followed by drying at 600℃ for half an hour. The dielectric property testing device is an impedance analyzer, and the piezoelectric property testing device is a piezoelectric constant tester. The polarization method is high-temperature oil bath polarization at 100~120℃ for 30~60 minutes.

[0089] The second aspect of this invention provides a multi-component piezoelectric ceramic with ultra-high energy harvesting performance that is photocured.

[0090] The third aspect of this invention provides an application of a photopolymerized, ultra-high energy harvesting performance multi-component piezoelectric ceramic in the field of energy harvesting.

[0091] It should be noted that, unless otherwise specified, the experimental methods used in this invention are all conventional methods; and the reagents and materials used, unless otherwise specified, are all commercially available.

[0092] The following examples provide a similar heat treatment process: room temperature - 300 min - 300 °C - 60 min - 300 °C - 400 min - 400 °C - 60 min - 400 °C - 200 min - 450 °C - 60 min - 450 °C - 250 min - 500 °C - 60 min - 500 °C - 250 min - 550 °C - 60 min - 550 °C - 250 min - 600 °C - 60 min - 600 °C ℃ indicates that the temperature is increased from room temperature to 300℃ after 300 minutes, held at 300℃ for 60 minutes, then increased to 400℃ for 400 minutes, held for 60 minutes, then increased to 450℃ for 200 minutes, held for 60 minutes, then increased to 500℃ for 250 minutes, held for 60 minutes, then increased to 550℃ for 250 minutes, held for 60 minutes, then increased to 600℃ for 250 minutes, and finally cooled with the furnace after 60 minutes.

[0093] The sequence "room temperature - 300 min - 300℃ - 60 min - 300℃ - 150 min - 450℃ - 60 min - 450℃ - 150 min - 600℃ - 60 min - 600℃ - 350 min - 1300℃ - 120 min - 1300℃" indicates that the temperature is raised from room temperature to 300℃ in 300 min, held at 300℃ for 60 min, then raised to 450℃ in 150 min, held for 120 min, then raised to 600℃ in 150 min, held for 120 min, then raised to 1300℃ in 350 min, held for 120 min, and then cooled with the furnace.

[0094] Example 1

[0095] Step 1. Accurately weigh the particle size d 50 One kilogram of PIN-PMN-PZ-PT nanoparticles (<200 nm) was added to a 1 L nylon ball milling jar containing anhydrous ethanol diluted with KH570 at a mass fraction of 2 wt% of the nanoparticles. The KH570 accounted for 5 wt% of the anhydrous ethanol, and the grinding beads were zirconia grinding beads, accounting for 25 wt% of the powder. The ball milling jar was placed in a planetary ball mill and ball milled at a speed of 350 r / min for 6 h.

[0096] Step 2. Open the lid of the ball milling jar after ball milling in Step 1, place it in an oven at 70°C to dry and evaporate the anhydrous ethanol for 24 hours. After drying and modifying, crush the nanoparticles through a 500-mesh sieve and weigh 800g of the sieved nanoparticles.

[0097] Step 3. Place the photocurable monomer resin (TMPTA, 120g, HDDA, 1,6-hexanediol diacrylate, 30g), soluble starch, dispersant (DISPERBYK-110, 10g, DISPERBYK-111, 5g), reactive diluent Triton X-100, defoamer Z-2006 ceramic slurry defoamer, photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and 200g of zirconia grinding beads into a 1L nylon ball mill jar. Set the ball milling speed to 500r / min and the ball milling time to 2h to obtain the organic polymer photocurable system.

[0098] Step 4. The 800g of nanoparticles weighed in Step 2 are gradually added to the polymer system in Step 3 in 8 portions. The ball mill jar is placed in a planetary ball mill for ball milling for 6 hours at a speed of 300 r / min. Finally, about 300ml of a photocurable slurry of a high solid content (80wt%) PIN-PMN-PZ-PT-organic polymer system with good stability, uniform dispersion and no obvious bubbles on the surface is obtained.

[0099] Step 5. Use SolidWorks software to draw the chiral torsion sandwich structure unit cell (e.g.) Figure 5 (As shown in a), the structural unit cells are then arrayed into a 10mm × 10mm rectangular area along the X and Y directions, with a unit cell height of 1.5mm. Two 0.25mm thick thin plates are added above and below the arrayed rectangular multi-unit cell array to facilitate subsequent electrode placement and polarization testing of electrical performance. Finally, the array is assembled and repaired using Magic software to obtain the photopolymer 3D printed superstructure model, as shown in a diagram. Figure 6 As shown in the lower left corner.

[0100] Step 6. Import the photocurable slurry prepared in Step 4 into the material tank of the photocurable printer, import the chiral torsion sandwich structure model, and enlarge the model by 1.35 times by calculating the shrinkage rate so that the designed size can be obtained after debinding and sintering. Set the single-layer slice thickness to 25 micrometers, the exposure current to 4000mA, the bottom layer exposure time to 20s, the number of bottom layers to 5, and the exposure time of the remaining parts to 12s.

[0101] Step 7. After ultrasonic cleaning with alcohol, the printed ceramic blank is placed in an oven at 80°C for 1 hour and then placed in a UV curing chamber for secondary curing to ensure that the resin in the blank is fully cured. Both sides of the blank need to be cured, and the curing time is set to 1 hour.

[0102] Step 8. Place the post-treated ceramic green body into a sintering furnace with an inert atmosphere (N2, Ar) for carbonization and debinding. Based on the thermogravimetric differential thermal curve of the green body, set the debinding rate as follows: room temperature - 300 min - 300℃ - 60 min - 300℃ - 400 min - 400℃ - 60 min - 400℃ - 200 min - 450℃ - 60 min - 450℃ - 250 min - 500℃ - 60 min - 500℃ - 250 min - 550℃ - 60 min - 550℃ - 250 min - 600℃ - 60 min - 600℃. After carbonization, the green body is placed in an air sintering furnace and then embedded in a covered alumina crucible using a powder embedding method. The decarburization and sintering process is as follows: room temperature - 300 min - 300℃ - 60 min - 300℃ - 150 min - 450℃ - 60 min - 450℃ - 150 min - 600℃ - 60 min - 600℃ - 350 min - 1300℃ - 120 min - 1300℃. This completes the debinding and sintering process, yielding a PIN-PMN-PZ-PT piezoelectric ceramic metamaterial with no warping deformation and good structural fidelity. SEM images are shown below. Figure 6 As shown in a.

[0103] Step 9. The obtained piezoelectric ceramic metamaterial is screen-printed with silver electrodes on both sides, then dried at 600℃ for 30 minutes. Its dielectric constant ε is measured using a precision impedance analyzer. r The value is 381. After polarization treatment by a polarization device, the piezoelectric constant d is measured in a piezoelectric constant tester. 33 The value is 524 pC / N, and the energy harvesting factor d is finally calculated. 33 ×g 33 81311×10 -15 m 2 / N, the result is as follows Figure 7 As shown.

[0104] Example 2

[0105] Step 1. Accurately weigh the particle size d 50 One kilogram of PIN-PMN-PZ-PT nanoparticles (<200 nm) was added to a 1 L nylon ball milling jar containing anhydrous ethanol diluted with KH570 at a mass fraction of 3 wt% of the nanoparticles. The KH570 accounted for 5 wt% of the anhydrous ethanol, and the grinding beads were zirconia grinding beads, accounting for 25 wt% of the powder. The ball milling jar was placed in a planetary ball mill and ball milled at a speed of 350 r / min for 6 h.

[0106] Step 2. Open the lid of the ball milling jar after ball milling in Step 1, place it in an oven at 70°C to dry and evaporate the anhydrous ethanol for 24 hours. After drying and modifying, crush the nanoparticles through a 500-mesh sieve and weigh 800g of the sieved nanoparticles.

[0107] Step 3. Place the photocurable monomer resin (epoxy acrylate EA, 100g, 1,6-hexanediol diacrylate HDDA, 50g), soluble starch 20g, dispersant (DISPERBYK-110, 10g, DISPERBYK-142, 5g), reactive diluent Triton X-100 5g, defoamer Z-2006 ceramic slurry defoamer 2g, photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819) 23g, and 200g of zirconia grinding beads into a 1L nylon ball mill jar. Set the ball milling speed to 500r / min and the ball milling time to 2h to obtain the organic polymer photocurable system.

[0108] Step 4. The 800g of nanoparticles weighed in Step 2 are gradually added to the polymer system in Step 3 in 8 portions. The ball mill jar is placed in a planetary ball mill for ball milling for 6 hours at a speed of 300 r / min. Finally, about 300ml of a photocurable slurry of a high solid content (80wt%) PIN-PMN-PZ-PT-organic polymer system with good stability, uniform dispersion and no obvious bubbles on the surface is obtained.

[0109] Step 5. Use SolidWorks software to draw the chiral torsion sandwich structure unit cell, then array the unit cells into a 10mm × 10mm rectangle along both the X and Y directions. The height of each unit cell is 1.5mm. Add two 0.25mm thick thin plates above and below the arrayed rectangular multi-unit cell array to facilitate subsequent electrode placement and polarization testing of electrical properties. Finally, assemble the components and perform repair processing in Magic software to obtain the photopolymer 3D printed superstructure model, as shown below. Figure 6 As shown in the lower left corner.

[0110] Step 6. Import the photocurable slurry prepared in Step 4 into the material tank of the photocurable printer, import the chiral torsion sandwich structure model, and enlarge the model by 1.35 times by calculating the shrinkage rate so that the designed size can be obtained after degreasing and sintering. Set the single-layer slice thickness to 20 micrometers, the exposure current to 3500mA, the bottom layer exposure time to 20s, the number of bottom layers to 5, and the exposure time of the remaining parts to 12s.

[0111] Step 7. After ultrasonic cleaning with alcohol, the printed ceramic blank is placed in an oven at 80°C for 1 hour and then placed in a UV curing chamber for secondary curing to ensure that the resin in the blank is fully cured. Both sides of the blank need to be cured, and the curing time is set to 1 hour.

[0112] Step 8. Place the post-treated ceramic green body into a sintering furnace with an inert atmosphere (N2, Ar) for carbonization and debinding. Based on the thermogravimetric differential thermal curve of the green body, set the debinding rate as follows: 300 min - 300℃ - 60 min - 300℃ - 400 min - 400℃ - 60 min - 400℃ - 200 min - 450℃ - 60 min - 450℃ - 250 min - 500℃ - 60 min - 500℃ - 250 min - 550℃ - 60 min - 550℃ - 250 min - 600℃ - 60 min ... At 0℃, after carbonization, the green body is placed in an air sintering furnace. The green body is then buried in a covered alumina crucible using the powder embedding method. The decarbonization and sintering process is as follows: 300 min - 300℃ - 60 min - 300℃ - 150 min - 450℃ - 60 min - 450℃ - 150 min - 600℃ - 60 min - 600℃ - 350 min - 1300℃ - 120 min - 1300℃. At this point, the debinding and sintering process is complete, resulting in a PIN-PMN-PZ-PT piezoelectric ceramic metamaterial with no warping deformation and good structural fidelity.

[0113] Step 9. The obtained piezoelectric ceramic metamaterial is screen-printed to coat both sides with silver electrodes, and then dried at 600℃ for 30 minutes to obtain the silver-coated piezoelectric ceramic metamaterial.

[0114] Example 3

[0115] Step 1. Accurately weigh the particle size d 50 One kilogram of PIN-PMN-PZ-PT nanoparticles (<200 nm) was added to a 1 L nylon ball milling jar containing anhydrous ethanol diluted with KH570 at a mass fraction of 4 wt% of the nanoparticles. The KH570 accounted for 5 wt% of the anhydrous ethanol, and the grinding beads were zirconia grinding beads, accounting for 25 wt% of the powder. The ball milling jar was placed in a planetary ball mill and ball milled at a speed of 350 r / min for 6 h.

[0116] Step 2. Open the lid of the ball milling jar after ball milling in Step 1, place it in an oven at 70°C to dry and evaporate the anhydrous ethanol for 24 hours. After drying and modifying, crush the nanoparticles through a 500-mesh sieve and weigh 800g of the sieved nanoparticles.

[0117] Step 3. Place the photocurable monomer resin (polyethylene glycol diacrylate PEGDA, 150g), soluble starch 23g, dispersant (DISPERBYK-110, 15g), reactive diluent Triton X-100 5g, defoamer Z-2006 ceramic slurry defoamer 2g, photoinitiator (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (819), 10g, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 10g) and 200g of zirconia grinding beads into a 1L nylon ball milling jar, set the ball milling speed to 500r / min, and the ball milling time to 2h to obtain the organic polymer photocurable system.

[0118] Step 4. The 800g of nanoparticles weighed in Step 2 are gradually added to the polymer system in Step 3 in 8 portions. The ball mill jar is placed in a planetary ball mill for ball milling for 6 hours at a speed of 300 r / min. Finally, about 300ml of a photocurable slurry of a high solid content (80wt%) PIN-PMN-PZ-PT-organic polymer system with good stability, uniform dispersion and no obvious bubbles on the surface is obtained.

[0119] Step 5. Use SolidWorks software to draw the chiral torsion sandwich structure unit cell, then array the unit cells into a 10mm × 10mm rectangle along both the X and Y directions. The height of each unit cell is 1.5mm. Add two 0.25mm thick thin plates above and below the arrayed rectangular multi-unit cell array to facilitate subsequent electrode placement and polarization testing of electrical properties. Finally, assemble the components and perform repair processing in Magic software to obtain the photopolymer 3D printed superstructure model, as shown below. Figure 6 As shown in the lower left corner.

[0120] Step 6. Import the photocurable slurry prepared in Step 4 into the material tank of the photocurable printer, import the chiral torsion sandwich structure model, and enlarge the model by 1.35 times by calculating the shrinkage rate so that the designed size can be obtained after degreasing and sintering. Set the single-layer slice thickness to 20 micrometers, the exposure current to 4500mA, the bottom layer exposure time to 20s, the number of bottom layers to 5, and the exposure time of the remaining parts to 12s.

[0121] Step 7. After ultrasonic cleaning with alcohol, the printed ceramic blank is placed in an oven at 80°C for 1 hour and then placed in a UV curing chamber for secondary curing to ensure that the resin in the blank is fully cured. Both sides of the blank need to be cured, and the curing time is set to 1 hour.

[0122] Step 8. Place the post-treated ceramic green body into a sintering furnace with an inert atmosphere (N2, Ar) for carbonization and debinding. Based on the thermogravimetric differential thermal curve of the green body, set the debinding rate as follows: 300 min - 300℃ - 60 min - 300℃ - 400 min - 400℃ - 60 min - 400℃ - 200 min - 450℃ - 60 min - 450℃ - 250 min - 500℃ - 60 min - 500℃ - 250 min - 550℃ - 60 min - 550℃ - 250 min - 600℃ - 60 min ... At 0℃, after carbonization, the green body is placed in an air sintering furnace. The green body is then buried in a covered alumina crucible using the powder embedding method. The decarbonization and sintering process is as follows: 300 min - 300℃ - 60 min - 300℃ - 150 min - 450℃ - 60 min - 450℃ - 150 min - 600℃ - 60 min - 600℃ - 350 min - 1300℃ - 120 min - 1300℃. At this point, the debinding and sintering process is complete, resulting in a PIN-PMN-PZ-PT piezoelectric ceramic metamaterial with no warping deformation and good structural fidelity.

[0123] Step 9. The obtained piezoelectric ceramic metamaterial is screen-printed to coat both sides with silver electrodes, and then dried at 600℃ for 30 minutes to obtain the silver-coated piezoelectric ceramic metamaterial.

[0124] Example 4

[0125] Step 1. Accurately weigh the particle size d 50 One kilogram of PIN-PMN-PZ-PT nanoparticles (<200 nm) was added to a 1 L nylon ball milling jar containing anhydrous ethanol diluted with KH570 at a mass fraction of 3 wt% of the nanoparticles. The KH570 accounted for 5 wt% of the anhydrous ethanol, and the grinding beads were zirconia grinding beads, accounting for 25 wt% of the powder. The ball milling jar was placed in a planetary ball mill and ball milled at a speed of 350 r / min for 6 h.

[0126] Step 2. Open the lid of the ball milling jar after ball milling in Step 1, place it in an oven at 70°C to dry and evaporate the anhydrous ethanol for 24 hours. After drying and modifying, crush the nanoparticles through a 500-mesh sieve and weigh 800g of the sieved nanoparticles.

[0127] Step 3. Place the photocurable monomer resin (90g of trimethylolpropane triacrylate (TMPTA), 30g of epoxy acrylate (EA), 30g of 1,6-hexanediol diacrylate (HDDA), 20g of soluble starch, 15g of dispersant (DISPERBYK-110), 5g of reactive diluent Triton X-100, 2g of defoamer Z-2006 ceramic slurry defoamer, 23g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and 200g of zirconia grinding beads into a 1L nylon ball milling jar. Set the ball milling speed to 500r / min and the ball milling time to 2h to obtain the organic polymer photocurable system.

[0128] Step 4. The 800g of nanoparticles weighed in Step 2 are gradually added to the polymer system in Step 3 in 8 portions. The ball mill jar is placed in a planetary ball mill for ball milling for 6 hours at a speed of 300 r / min. Finally, about 300ml of a photocurable slurry of a high solid content (80wt%) PIN-PMN-PZ-PT-organic polymer system with good stability, uniform dispersion and no obvious bubbles on the surface is obtained.

[0129] Step 5. Use SolidWorks software to draw the body-centered cubic sandwich structure unit cell (e.g., Figure 5 (As shown in b), the structural unit cells are then arrayed into a 10mm × 10mm rectangular area along the X and Y directions, with a unit cell height of 1.5mm. Two 0.25mm thick thin plates are added above and below the arrayed rectangular multi-unit cell array to facilitate subsequent electrode placement and polarization testing of electrical performance. Finally, the array is assembled and repaired using Magic software to obtain the photopolymer 3D printed superstructure model, as shown in b. Figure 6 b is shown in the lower left corner.

[0130] Step 6. Import the photocurable slurry prepared in Step 4 into the material tank of the photocurable printer, import the body-centered cubic sandwich structure model, and enlarge the model by 1.35 times by calculating the shrinkage rate so that the designed size can be obtained after debinding and sintering. Set the single-layer slice thickness to 25 micrometers, the exposure current to 4000mA, the bottom layer exposure time to 20s, the number of bottom layers to 5, and the exposure time of the remaining parts to 12s.

[0131] Step 7. After ultrasonic cleaning with alcohol, the printed ceramic blank is placed in an oven at 80°C for 1 hour and then placed in a UV curing chamber for secondary curing to ensure that the resin in the blank is fully cured. Both sides of the blank need to be cured, and the curing time is set to 1 hour.

[0132] Step 8. Place the post-treated ceramic green body into a sintering furnace with an inert atmosphere (N2, Ar) for carbonization and debinding. Based on the thermogravimetric differential thermal curve of the green body, set the debinding rate as follows: 300 min - 300℃ - 60 min - 300℃ - 400 min - 400℃ - 60 min - 400℃ - 200 min - 450℃ - 60 min - 450℃ - 250 min - 500℃ - 60 min - 500℃ - 250 min - 550℃ - 60 min - 550℃ - 250 min - 600℃ - 60 min - 600℃. After carbonization, the green body is placed in an air sintering furnace and then embedded in a covered alumina crucible using a powder embedding method. The decarburization and sintering process is as follows: 300 min - 300℃ - 60 min - 300℃ - 150 min - 450℃ - 60 min - 450℃ - 150 min - 600℃ - 60 min - 600℃ - 350 min - 1300℃ - 120 min - 1300℃. This completes the debinding and sintering process, yielding a PIN-PMN-PZ-PT piezoelectric ceramic metamaterial with no warping deformation and good structural fidelity. SEM images are shown below. Figure 6 As shown in b.

[0133] Step 9. The obtained piezoelectric ceramic metamaterial is screen-printed with silver electrodes on both sides, then dried at 600℃ for 30 minutes. Its dielectric constant ε is measured using a precision impedance analyzer. r The piezoelectric constant d is 244, and after polarization treatment by a polarization device, it is measured in a piezoelectric constant tester. 33 The value is 572 pC / N, and the energy harvesting factor d is finally calculated. 33 ×g 33 151233×10 -15 m 2 / N exhibits excellent energy harvesting performance, exploring the application potential of photopolymerization structures in the field of energy harvesting, with results as follows: Figure 7 As shown.

[0134] Example 5

[0135] Step 1. Accurately weigh the particle size d 50 One kilogram of PIN-PMN-PZ-PT nanoparticles (<200 nm) was added to a 1 L nylon ball mill jar containing an anhydrous ethanol dilution solution of KH570 (2.5 wt% of the nanoparticles by mass), wherein KH570 accounted for 5 wt% of the anhydrous ethanol and the grinding beads were zirconia grinding beads, accounting for 25 wt% of the powder by mass. The ball mill jar was placed in a planetary ball mill and ball milled at a speed of 350 r / min for 6 h.

[0136] Step 2. Open the lid of the ball milling jar after ball milling in Step 1, place it in an oven at 70°C to dry and evaporate the anhydrous ethanol for 24 hours. After drying and modifying, crush the nanoparticles through a 500-mesh sieve and weigh 800g of the sieved nanoparticles.

[0137] Step 3. Place the photocurable monomer resin (90g of trimethylolpropane triacrylate TMPTA, 30g of 1,6-hexanediol diacrylate HDDA), 20g of soluble starch, 15g of dispersant (DISPERBYK-142), 5g of reactive diluent Triton X-100, 2g of defoamer Z-2006 ceramic slurry defoamer, 23g of photoinitiator (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (819)) and 200g of zirconia grinding beads into a 1L nylon ball milling jar, set the ball milling speed to 500r / min, and the ball milling time to 2h to obtain the organic polymer photocurable system.

[0138] Step 4. The 800g of nanoparticles weighed in Step 2 are gradually added to the polymer system in Step 3 in 8 portions. The ball mill jar is placed in a planetary ball mill for ball milling for 6 hours at a speed of 300 r / min. Finally, about 300ml of a photocurable slurry of a high solid content (80wt%) PIN-PMN-PZ-PT-organic polymer system with good stability, uniform dispersion and no obvious bubbles on the surface is obtained.

[0139] Step 5. Using SolidWorks software, draw the straight-bar array sandwich structure unit cell, i.e., a single cylinder. Then, array the unit cells in a 10mm × 10mm rectangular area along the X and Y directions. The height of each unit cell is 1.5mm. Add two 0.25mm thick thin plates above and below the arrayed rectangular multi-unit cell array to facilitate subsequent electrode placement and polarization testing of electrical performance. Finally, assemble the components and perform repair processing in Magic software to obtain the photopolymer 3D printed superstructure model, as shown below. Figure 6 As shown in the lower left corner of c, each rod of the straight rod array sandwich structure is independent, making it the most difficult to solidify among the aforementioned structures, with a single rod diameter of 300 micrometers.

[0140] Step 6. Import the photocurable slurry prepared in Step 4 into the material tank of the photocurable printer, import the straight rod array sandwich structure model, and enlarge the model by 1.35 times by calculating the shrinkage rate so that the designed size can be obtained after degreasing and sintering. Set the single-layer slice thickness to 25 micrometers, the exposure current to 5000mA, the bottom layer exposure time to 20s, the number of bottom layers to 5, and the exposure time of the remaining parts to 15s.

[0141] Step 7. After ultrasonic cleaning with alcohol, the printed ceramic blank is placed in an oven at 80°C for 1 hour and then placed in a UV curing chamber for secondary curing to ensure that the resin in the blank is fully cured. Both sides of the blank need to be cured, and the curing time is set to 1 hour.

[0142] Step 8. Place the post-treated ceramic green body into a sintering furnace with an inert atmosphere (N2, Ar) for carbonization and debinding. Based on the thermogravimetric differential thermal curve of the green body, set the debinding rate as follows: 300 min - 300℃ - 60 min - 300℃ - 400 min - 400℃ - 60 min - 400℃ - 200 min - 450℃ - 60 min - 450℃ - 250 min - 500℃ - 60 min - 500℃ - 250 min - 550℃ - 60 min - 550℃ - 250 min - 600℃ - 60 min - 600℃. After carbonization, the green body is placed in an air sintering furnace and then embedded in a covered alumina crucible using a powder embedding method. The decarburization and sintering process is as follows: 300 min - 300℃ - 60 min - 300℃ - 150 min - 450℃ - 60 min - 450℃ - 150 min - 600℃ - 60 min - 600℃ - 350 min - 1300℃ - 120 min - 1300℃. This completes the debinding and sintering process, yielding a PIN-PMN-PZ-PT piezoelectric ceramic metamaterial with no warping deformation and good structural fidelity. SEM images are shown below. Figure 6 As shown in c.

[0143] Step 9. The obtained piezoelectric ceramic metamaterial is screen-printed with silver electrodes on both sides, then dried at 600℃ for 30 minutes. Its dielectric constant ε is measured using a precision impedance analyzer. r The piezoelectric constant d is 530, and after polarization treatment by a polarization device, it is measured in a piezoelectric constant tester. 33 The value is 530 pC / N, and the energy harvesting factor d is finally calculated. 33 ×g 33 59829×10 -15 m 2 / N, the result is as follows Figure 7 As shown.

[0144] It should be noted that if the unstructured piezoelectric ceramic sample is prepared by dry pressing (i.e., a pure cube sample with the same length, width, and height), its dielectric constant ε r The measured value is 2342, and the piezoelectric constant d is... 33 The value is 580 pC / N, and the energy harvesting factor d is finally calculated. 33 ×g 33 16223×10 -15 m 2 / N, while the prepared body-centered cubic sandwich structure can reach 151233×10-15 m 2 / N is nearly 10 times that of the unstructured sample, therefore the piezoelectric ceramic superstructure designed in this invention greatly explores the potential of macroscopic structure design in the field of energy harvesting.

[0145] In summary, PIN-PMN-PZ-PT based piezoelectric ceramics exhibit high absorbance in the ultraviolet wavelength range. The layer-by-layer absorption and scattering caused by the high-performance nanoparticles result in poor curing ability of PIN-PMN-PZ-PT nanoparticles compared to other piezoelectric ceramics. However, this invention directly formulates a photocurable slurry while maintaining the original nanoparticle size. Therefore, the problem solved by this invention can also be applied to other types of piezoelectric nanoparticles. Similarly, PIN-PMN-PZ-PT has a high density and exhibits good curing ability at high solid content (>40 vol%). The required mass percentage is very high. This invention can maintain suitable viscosity and dispersibility of the slurry and is also applicable to other materials. The designed piezoelectric ceramic metamaterial structure is very suitable for photopolymerization 3D printing process, especially for subsequent electrode placement and performance testing processes. It can maximize the restoration of the influence of macro- and micro-structures on the intrinsic electrical properties of piezoelectric ceramics. The three designed structures all have high piezoelectric performance, and the structure mass percentage is only 20% of the pure cube sample, realizing the lightweight preparation of piezoelectric ceramics. The highest energy harvesting factor reached 151233.9×10 -15 m 2 / N has excellent energy harvesting performance, has significant advantages in the field of energy harvesting, and has significant application and theoretical value.

[0146] This invention describes preferred embodiments and their effects. However, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to include both the preferred embodiments and all changes and modifications falling within the scope of this invention.

[0147] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a multicomponent piezoelectric ceramic with super-high energy harvesting performance by light-curing molding, characterized in that, The method comprises the following steps: Preparation of PIN-PMN-PZ-PT nanoparticles; The PIN-PMN-PZ-PT nanoparticles are added into a surface modification solution and treated by ball milling to obtain surface-functionalized PIN-PMN-PZ-PT nanoparticles; A photosensitive resin organic polymer system is obtained by uniformly mixing a photocuring monomer resin, soluble starch, dispersant, active diluent and defoaming agent; PIN-PMN-PZ-PT-based piezoelectric ceramic slurry is obtained by adding the surface-functionalized PIN-PMN-PZ-PT nanoparticles into the photosensitive resin organic polymer system in batches, ball milling, and then adding a photoinitiator and continuing the ball milling; A three-dimensional structure model of a three-dimensional periodic complex structure is designed; The PIN-PMN-PZ-PT-based piezoelectric ceramic slurry is poured into a trough of a photocuring printer, the three-dimensional structure model is imported into the photocuring printer, printing parameters are set, and a green body is obtained by printing; After the green body is subjected to debinding and sintering, a piezoelectric ceramic is obtained; The surface modification solution is prepared by dissolving a silane coupling agent in ethanol; The silane coupling agent is γ-glycidoxypropyltrimethoxysilane or γ-methacryloyloxypropyltrimethoxysilane; The mass fraction of the silane coupling agent in the surface modification solution is 4-6%; The PIN-PMN-PZ-PT nanoparticle content in the PIN-PMN-PZ-PT-based piezoelectric ceramic slurry is 80-85wt%; the particle size d 50 <200nm; The photocuring monomer resin is one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate and epoxy acrylate; the addition amount of the photocuring monomer resin accounts for 10-15wt% of the PIN-PMN-PZ-PT-based piezoelectric ceramic slurry; The dispersant is one or more of DISPERBYK-110, DISPERBYK-142 and DISPERBYK-111; The addition amount of the dispersant accounts for 1-3wt% of the PIN-PMN-PZ-PT-based piezoelectric ceramic slurry; The active diluent is Triton X-100; the addition amount of the active diluent accounts for 0.5-1wt% of the PIN-PMN-PZ-PT-based piezoelectric ceramic slurry; The defoaming agent is Z-2006 ceramic slurry defoaming agent; the addition amount of the defoaming agent accounts for 0.1-0.3wt% of the PIN-PMN-PZ-PT-based piezoelectric ceramic slurry; The addition amount of the soluble starch accounts for 10-20vol% of the volume fraction of the PIN-PMN-PZ-PT nanoparticles; The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and / or phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide; the addition amount of the photoinitiator accounts for 5-20wt% of the photocuring monomer resin. The defatting process comprises: under inert atmosphere, heating to 300℃ at room temperature for 300 min, keeping at 300℃ for 60 min, then heating to 400℃ for 400 min, keeping at 400℃ for 60 min, then heating to 450℃ for 200 min, keeping at 450℃ for 60 min, then heating to 500℃ for 250 min, keeping at 500℃ for 60 min, then heating to 550℃ for 250 min, keeping at 550℃ for 60 min, then heating to 600℃ for 250 min, keeping at 600℃ for 60 min, then furnace cooling, removing O and H elements; The sintering process comprises: in air, heating to 300℃ at room temperature for 300 min, keeping at 300℃ for 60 min, then heating to 450℃ for 150 min, keeping at 450℃ for 120 min, then heating to 600℃ for 150 min, keeping at 600℃ for 120 min, then heating to 1300℃ for 350 min, keeping at 1300℃ for 120 min, then furnace cooling.

2. The method of claim 1, wherein the method is a method of preparing a multicomponent piezoelectric ceramic having an ultrahigh energy harvesting performance through a photocuring molding process, the method comprising: preparing a slurry by mixing a piezoelectric ceramic powder, a binder, a solvent, and a dispersant; coating the slurry on a substrate; and drying the slurry coated on the substrate. The surface modification solution is added in an amount of 1-5 wt% of the mass of the PIN-PMN-PZ-PT nanoparticles.

3. The method of claim 1, wherein the method is a method of preparing a multicomponent piezoelectric ceramic having a super-high energy harvesting performance through a photo-curing molding process, the method comprising: preparing a slurry by mixing a piezoelectric ceramic powder, a binder, a solvent, and a dispersant; coating the slurry on a substrate; and drying the slurry coated on the substrate. The printing parameters are: single layer thickness of 15-30 μm, exposure current of 2000-5000 mA, exposure time of 5-15 s per layer, and scraper speed of 800 step / s.

4. A light-cured molding super-high energy harvesting performance multinary piezoelectric ceramic prepared by the method of any one of claims 1-3.

5. Application of the light-cured molding super-high energy harvesting performance multinary piezoelectric ceramic of claim 4 in the field of energy harvesting.

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