Chiral hybrid perovskite piezoelectric crystal material and preparation method and application thereof
The non-center symmetric chiral hybrid perovskite piezoelectric crystal is prepared through organic-inorganic hybridization of chiral organic amine and rubidium iodide, which solves the problem of high energy consumption and toxic metals in the synthesis of piezoelectric materials, and achieves materials with high thermal stability and excellent piezoelectric properties, which are suitable for flexible electronic devices.
Patent Information
- Application Number
- CN202510597437.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-09
- Publication Date
- 2025-08-08
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing piezoelectric material synthesis process has high energy consumption, poor thermal stability and piezoelectric properties, and contains toxic metals, which limits its application in flexible electronics and other fields.
The chiral organic amine (R)-(+)-3-aminoquinine cyclodihydrochloride and rubidium iodide were used to hybridize organic-inorganic to form a non-center symmetric chiral hybrid perovskite piezoelectric crystal material, which was prepared by the room temperature solvent volatilization method.
The prepared materials have high thermal stability and excellent piezoelectric properties, no toxic metals required, and are suitable for flexible electronic devices, simplifying the synthesis process and reducing environmental pollution.
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Figure CN120443336A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of functional hybrid materials, and in particular to a chiral hybrid perovskite piezoelectric crystal material and a preparation method and application thereof. Background Art
[0002] Piezoelectric crystals are dielectric crystals that can generate polarization. Mechanical stimulation can produce charge displacement, resulting in a net positive and negative charge on the crystal surface and a potential difference across the crystal. This property is known as direct piezoelectricity. Conversely, these crystals can also produce macroscopic deformation when an electric field is applied, a property known as the inverse piezoelectric effect. The inverse piezoelectric effect is central to many electronic technologies and has potential applications in television circuits, mobile phone RF front-end modules, and computer motherboards. The definition of a piezoelectric material dictates that the crystal exhibit spontaneous polarization, which means it should not have a center of symmetry. Of the 32 point groups, 11 are centrosymmetric. Of the remaining 21 non-centrosymmetric point groups, all but 432 exhibit piezoelectricity, resulting in a total of 20 piezoelectric point groups. Currently, inorganic piezoelectric ceramics are widely used, offering high piezoelectric coefficients and a wide range of coefficient distribution. They are used in underwater acoustic transducers, ultrasonic testing, and other applications. The design and synthesis of novel piezoelectric materials is of great significance for both basic research and practical applications.
[0003] Piezoelectric materials are mainly divided into three categories: inorganic materials, organic materials, and hybrid organic-inorganic materials. Inorganic piezoelectric materials mainly include perovskite oxides such as lead zirconate titanate and barium titanate. These materials have excellent and stable piezoelectric properties, high dielectric constants and mechanical strength, but their synthesis process is relatively energy-intensive. These materials are widely used in fields such as filters, ultrasonic transducers, and piezoelectric sensors. Organic piezoelectric materials mainly include polyvinylidene chloride (PVDF) and its copolymers. These piezoelectric materials have advantages such as easy processing, low density, low acoustic impedance, and a high piezoelectric voltage constant, but they have poor thermal stability and piezoelectricity. They are mainly used in underwater acoustic transducers, ultrasonic transducers, and pressure sensors. Hybrid organic-inorganic piezoelectric materials mainly include hybrid organic-inorganic perovskites and metal-organic frameworks (MOFs). They have the advantages of easy synthesis, light weight, low acoustic impedance, good biocompatibility, and strong designability. Some hybrid organic-inorganic piezoelectric materials have piezoelectric properties comparable to those of piezoelectric ceramics, and therefore have great application potential in fields such as nano-energy conversion, flexible wearable devices, and catalysis.
[0004] Hybrid organic-inorganic piezoelectric crystal materials have great application potential in the fields of electromechanical conversion, acoustic wave detection and acoustic detection, and have attracted widespread attention. In 2019, researchers Xiong et al. discovered that molecular solid solution (TMFM) x (TMCM) 1-x-CdCl3 has a large d33 value of 1540pC / N. In addition, the researchers also found that the two-dimensional perovskite material (ATHP) 2PbBr4 has a large g33 value of 660.3×10 -3 Vm / N, these values are much higher than those of existing commercial piezoelectric materials, such as PZT-5H (d33=593pC / N) and PVDF (g33=286.7×10 -3 Vm / N). Currently, hybrid organic-inorganic piezoelectric materials have great potential for development in the field of flexible electronics, and this property is often accompanied by other important properties, such as excellent mechanical properties, good stability, strong plasticity and high elasticity. However, the relevant piezoelectric crystal materials reported so far often contain Pb 2+ 、Cd 2+ Toxic metals greatly hinder their application in smart sensing, flexible electronics and other fields. Summary of the Invention
[0005] The present invention provides a chiral hybrid perovskite piezoelectric crystal material and a preparation method and application thereof, which effectively solves the technical problems of energy consumption in the synthesis process of existing piezoelectric materials, poor thermal stability and piezoelectric performance, the presence of toxic metals, and severe environmental pollution. The present invention uses chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride as a ligand and obtains a non-centrosymmetric chiral hybrid perovskite piezoelectric crystal by organic-inorganic hybridization with rubidium iodide.
[0006] The first object of the present invention is to provide a chiral hybrid perovskite piezoelectric crystal material, which is prepared by organic-inorganic hybridization of chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride and rubidium iodide, wherein any Rb + The ion coordinates with six adjacent iodide ions to form an octahedron, and the octahedra form a perovskite framework by sharing corners. The cavity of the perovskite framework is occupied by the (R)-(+)-3-aminoquinuclidine cation.
[0007] The chiral organic-inorganic hybrid perovskite piezoelectric crystal material is non-centrosymmetric, its space group is P3121, and the crystal cell parameters are: α=90°, β=120°, γ=90°.
[0008] A second object of the present invention is to provide a method for preparing the chiral hybrid perovskite piezoelectric crystal material, comprising the following steps:
[0009] Chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride is used as a ligand, rubidium iodide is used as a raw material, and they are mixed with a hydroiodic acid aqueous solution. The chiral organic-inorganic hybrid perovskite piezoelectric crystal material is obtained by a room temperature solvent evaporation method.
[0010] As a preferred embodiment, the molar ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to rubidium iodide is 1:1-2.
[0011] As a preferred embodiment, after mixing, hypophosphorous acid is added, and the usage ratio of rubidium iodide to hypophosphorous acid is 1 mol:0.3-0.6 mL.
[0012] As a preferred embodiment, the concentration of the hydroiodic acid aqueous solution is 0.56 g / mL to 0.85 g / mL, and the ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to the hydroiodic acid aqueous solution is 1 mol:2 mL.
[0013] As a preferred embodiment, a chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride is added to an aqueous rubidium iodide solution, and then an aqueous hydroiodic acid solution is added. The mixture is ultrasonicated at room temperature and the solvent is removed to obtain a chiral organic-inorganic hybrid perovskite piezoelectric crystal material.
[0014] As a preferred embodiment, the solvent removal comprises: standing at room temperature for 4 to 5 days.
[0015] The third object of the present invention is to provide an application of the chiral hybrid perovskite piezoelectric crystal material in a piezoelectric device.
[0016] Compared with the prior art, the present invention has the following beneficial effects:
[0017] The present invention provides a chiral hybrid perovskite piezoelectric crystal material. A non-centrosymmetric chiral hybrid perovskite piezoelectric crystal is prepared by organic-inorganic hybridization with rubidium iodide using a chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride as a ligand. When an exciter and ultrasonic waves are applied to the surface of the non-centrosymmetric chiral hybrid perovskite piezoelectric crystal material prepared by the present invention, polarization occurs within the crystal, and opposite positive and negative charges appear on two opposing surfaces of the crystal. An oscilloscope is connected to observe the magnitude of the generated voltage signal. When the external force is removed, the crystal returns to an uncharged state, and the oscilloscope reading is zero, thereby demonstrating that the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention has piezoelectric properties. Furthermore, the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention has high thermal stability.
[0018] The present invention dissolves a mixture of rubidium iodide and a chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride in deionized water and hydroiodic acid, then sonicates at room temperature until the solution gradually clarifies. Hypophosphorous acid is then added dropwise to prevent oxidation of iodide ions. The solution is then allowed to stand at room temperature to volatilize the solvent. After several days, colorless, transparent block crystals are obtained, which are then filtered and dried to obtain a chiral hybrid perovskite piezoelectric crystal material. The present invention utilizes a room-temperature volatilization method, resulting in a simple and efficient preparation method, a simple operation process, low cost, high purity of the target product, high thermal stability of the product, and minimal environmental pollution. This method lays a foundation for the development and application of novel hybrid organic-inorganic materials in the field of sensing. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 This is the PXRD pattern of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention, wherein Obs=actual value, Calc=calculated value, and Diff=the difference between the actual value and the calculated value.
[0020] Figure 2 This is a structural diagram of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention.
[0021] Figure 3 This is the thermogravimetric image of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention.
[0022] Figure 4 These are the three-dimensional and two-dimensional piezoelectric tensor distribution diagrams of the chiral hybrid piezoelectric crystal material prepared in Example 1 of the present invention, wherein Figure A is the three-dimensional piezoelectric tensor distribution diagram, and Figure B is the two-dimensional piezoelectric tensor distribution diagram.
[0023] Figure 5 This is a test diagram of the piezoelectric voltage output performance of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention under the action of an exciter.
[0024] Figure 6 This is a test diagram of the piezoelectric voltage output performance of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention under the action of ultrasound. DETAILED DESCRIPTION
[0025] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention is further described below with reference to specific examples, but the examples are not intended to limit the present invention. The following experimental and detection methods are conventional methods unless otherwise specified; the reagents and raw materials are commercially available unless otherwise specified.
[0026] Compared with existing piezoelectric materials, inorganic piezoelectric materials have superior and stable piezoelectric properties, high dielectric constant and mechanical strength, but have the disadvantage of being relatively energy-consuming to synthesize. Organic piezoelectric materials have advantages such as easy processing, low density, low acoustic impedance and high piezoelectric voltage constant, but they perform poorly in terms of thermal stability and piezoelectricity. Hybrid organic-inorganic piezoelectric crystal materials contain toxic metals, which pollute the environment. The present invention provides a chiral hybrid perovskite piezoelectric crystal material, a preparation method and application thereof.
[0027] The technical solution of the present invention is described in detail below.
[0028] The present invention provides a chiral hybrid perovskite piezoelectric crystal material, which is prepared by organic-inorganic hybridization of chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride and rubidium iodide. In the chiral hybrid perovskite piezoelectric crystal material, any Rb + The ion coordinates with six adjacent iodide ions to form an octahedron, and the octahedra form a perovskite framework by sharing corners. The cavity of the perovskite framework is occupied by the (R)-(+)-3-aminoquinuclidine cation.
[0029] The chiral organic-inorganic hybrid perovskite piezoelectric crystal material is non-centrosymmetric, its space group is P3121, and the crystal cell parameters are: α=90°, β=120°, γ=90°.
[0030] For the chiral hybrid perovskite piezoelectric crystal material provided above by the present invention, when an exciter and ultrasound are applied to the surface of the chiral hybrid perovskite piezoelectric crystal material, polarization occurs inside the crystal, and opposite positive and negative charges appear on the two opposite surfaces of the crystal. The magnitude of the voltage signal generated can be observed by connecting an oscilloscope. When the external force is removed, the crystal returns to an uncharged state, and the oscilloscope reading is zero. Therefore, the chiral hybrid perovskite piezoelectric crystal material has piezoelectric properties. In addition, the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention has high thermal stability.
[0031] The present invention also provides a method for preparing the chiral hybrid perovskite piezoelectric crystal material, comprising the following steps:
[0032] Chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride is used as a ligand, and rubidium iodide is used as a raw material.
[0033] Rubidium iodide is dissolved in a deionized water solution, and the rubidium iodide is dissolved by ultrasound at room temperature to obtain a solution A.
[0034] Chiral organic amine ligand (R)-(+)-3-aminoquinuclidine dihydrochloride is added to solution A, hydroiodic acid aqueous solution is added, ultrasonication is performed at room temperature, and hypophosphorous acid is added to obtain a clear solution B.
[0035] The clear solution B is placed in a room temperature environment and allowed to stand to obtain colorless transparent bulk crystals. The bulk crystals are filtered and then dried to obtain a chiral hybrid perovskite piezoelectric crystal material.
[0036] In order to successfully prepare a chiral organic-inorganic hybrid perovskite piezoelectric crystal material, the molar ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to rubidium iodide is 1:1 to 2. When the molar ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to rubidium iodide is 1:1, the chiral hybrid perovskite piezoelectric crystal material can be synthesized. Considering that organic amines are relatively expensive, in order to improve the conversion rate, the amount of rubidium iodide can be increased, and the molar ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to rubidium iodide is limited to 1:1 to 2.
[0037] In order to prevent the iodide ions in the reaction system from being oxidized, thereby affecting the purity of the product, hypophosphorous acid is added after mixing. The dosage ratio of rubidium iodide to hypophosphorous acid is 1 mol:0.3 mL~0.6 mL. When the dosage ratio of rubidium iodide to hypophosphorous acid is 1 mol:0.5 mL, the effect is best.
[0038] It should be noted that the concentration of the hydroiodic acid aqueous solution used in the present invention is 0.56 g / mL to 0.85 g / mL, and the ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to the hydroiodic acid aqueous solution is 1 mol:2 mL.
[0039] In order to prepare a chiral hybrid perovskite piezoelectric crystal material, a chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride was added to an aqueous rubidium iodide solution, followed by an aqueous hydroiodic acid solution. The solution was ultrasonicated at room temperature and allowed to stand at room temperature for 4 to 5 days. After the solvent evaporated, a chiral organic-inorganic hybrid perovskite piezoelectric crystal material was obtained.
[0040] The present invention will be described in detail below through the following examples and comparative examples.
[0041] Example 1
[0042] A method for preparing a chiral hybrid perovskite piezoelectric crystal material comprises the following steps:
[0043] S1. Weigh 1 mmol (212.4 mg) of rubidium iodide into a 25 mL beaker. Use a pipette to take 4 mL of deionized water and slowly add it to the beaker. Seal the beaker and sonicate at room temperature for 2 min to completely dissolve the rubidium iodide to obtain solution A.
[0044] S2. Add 1 mmol (199 mg) of (R)-(+)-3-aminoquinuclidine dihydrochloride to the solution A, add 2 mL of hydroiodic acid with a concentration of 0.72 g / mL using a 1 mL to 5 mL pipette, dissolve it by ultrasonication at room temperature, and add 0.5 mL of hypophosphorous acid dropwise. Then, place it in a room temperature environment, let it stand for 4 d to 5 d, filter to obtain a primary product, wash the primary product, and dry it in an oven at 55 ° C for 2 h to obtain a chiral hybrid perovskite piezoelectric crystal material.
[0045] Example 2
[0046] A method for preparing a chiral hybrid perovskite piezoelectric crystal material comprises the following steps:
[0047] S1. Weigh 2 mmol (424.8 mg) of rubidium iodide into a 25 mL beaker. Use a pipette to take 4 mL of deionized water and slowly add it to the beaker. Seal the beaker and sonicate at room temperature for 2 min to completely dissolve the rubidium iodide to obtain solution A.
[0048] S2. Add 1 mmol (199 mg) of (R)-(+)-3-aminoquinuclidine dihydrochloride to the solution A, add 2 mL of hydroiodic acid with a concentration of 0.72 g / mL using a 1 mL to 5 mL pipette, dissolve it by ultrasonication at room temperature, and add 0.5 mL of hypophosphorous acid dropwise. Then, place it in a room temperature environment, let it stand for 4 d to 5 d, filter to obtain a primary product, wash the primary product, and dry it in an oven at 55 ° C for 2 h to obtain a chiral hybrid perovskite piezoelectric crystal material.
[0049] Example 3
[0050] S1. Weigh 1.5 mmol (318.6 mg) of rubidium iodide into a 25 mL beaker. Use a pipette to take 4 mL of deionized water and slowly add it to the beaker. Seal the beaker and sonicate at room temperature for 2 min to completely dissolve the rubidium iodide to obtain solution A.
[0051] S2. Add 1 mmol (199 mg) of (R)-(+)-3-aminoquinuclidine dihydrochloride to the solution A, add 2 mL of hydroiodic acid with a concentration of 0.72 g / mL using a 1 mL to 5 mL pipette, dissolve it by ultrasonication at room temperature, and add 0.5 mL of hypophosphorous acid dropwise. Then, place it in a room temperature environment, let it stand for 4 d to 5 d, filter to obtain a primary product, wash the primary product, and dry it in an oven at 55 ° C for 2 h to obtain a chiral hybrid perovskite piezoelectric crystal material.
[0052] Example 4
[0053] A method for preparing a chiral hybrid perovskite piezoelectric crystal material comprises the following steps:
[0054] S1. Weigh 1 mmol (212.4 mg) of rubidium iodide into a 25 mL beaker. Use a pipette to take 4 mL of deionized water and slowly add it to the beaker. Seal the beaker and sonicate at room temperature for 2 min to completely dissolve the rubidium iodide to obtain solution A.
[0055] S2. Add 1 mmol (199 mg) of (R)-(+)-3-aminoquinuclidine dihydrochloride to the solution A, add 2 mL of hydroiodic acid with a concentration of 0.72 g / mL using a 1 mL to 5 mL pipette, dissolve it by ultrasonication at room temperature, and add 0.3 mL of hypophosphorous acid dropwise. Then, place it in a room temperature environment, let it stand for 4 to 5 days, filter to obtain a primary product, wash the primary product, and dry it in an oven at 55°C for 2 hours to obtain a chiral hybrid perovskite piezoelectric crystal material.
[0056] Example 5
[0057] A method for preparing a chiral hybrid perovskite piezoelectric crystal material comprises the following steps:
[0058] S1. Weigh 1 mmol (212.4 mg) of rubidium iodide into a 25 mL beaker. Use a pipette to take 4 mL of deionized water and slowly add it to the beaker. Seal the beaker and sonicate at room temperature for 2 min to completely dissolve the rubidium iodide to obtain solution A.
[0059] S2. Add 1 mmol (199 mg) of (R)-(+)-3-aminoquinuclidine dihydrochloride to the solution A, add 2 mL of hydroiodic acid with a concentration of 0.72 g / mL using a 1 mL to 5 mL pipette, dissolve it by ultrasonication at room temperature, and add 0.6 mL of hypophosphorous acid dropwise. Then, place it in a room temperature environment, let it stand for 4 to 5 days, filter to obtain a primary product, wash the primary product, and dry it in an oven at 55°C for 2 hours to obtain a chiral hybrid perovskite piezoelectric crystal material.
[0060] The chiral hybrid perovskite piezoelectric crystal material provided in the above embodiment was characterized and its performance was tested, and the results are as follows.
[0061] The chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention was characterized by XRD powder diffraction, with a maximum voltage of 40KV. Turn on the instrument switch, then open the MiniFlex Guidance software and perform aging. Place the sample on a clean silicon wafer, flatten it with a scraper, press the "Door Lock" button, and open the door after two beeps. Place the silicon wafer with the sample, close the door, set the test conditions, the scanning speed is 3° / min, and the 2θ is 5°~50°. The results are as follows: Figure 1As shown. Figure 1 It can be clearly seen that the XRD pattern of the crystal is almost consistent with the fitting result of the theoretical calculated value, indicating that the purity of the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention is very high.
[0062] The structure of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention is shown in FIG. Figure 2 The target compound has a typical perovskite structure. + The ion coordinates with the six adjacent iodide ions to form an octahedron, which is expanded into a perovskite framework by sharing corners. The perovskite cavity is occupied by the (R)-(+)-3-aminoquinuclidine cation.
[0063] The thermal stability of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 was tested using a thermogravimetric analyzer. 8 mg of sample was weighed and the test was performed in air atmosphere with a scanning range of 25°C to 800°C and a scanning rate of 10°C / min. The results are shown in Figure 2. Figure 3 As shown, from Figure 3 It can be clearly seen that the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention has good thermal stability and a decomposition temperature of 320°C.
[0064] The piezoelectric parameters and distribution of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 were calculated using density functional theory. The results are as follows: Figure 4 The results show that the target crystal has two piezoelectric coefficients d 11 and d 14 , their values are -4.04 pC / N and 14.54 pC / N, respectively. This shows that the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention has a large shear piezoelectricity.
[0065] 100 mg of the chiral hybrid perovskite piezoelectric crystal material prepared in Example 1 of the present invention was dissolved in 5 mL of deionized water to prepare a solution with a concentration of 20 mg / mL. 300 μL of the above solution was drop-coated on a commercial PET substrate coated with PEDOT:PSS. The PET substrate was placed on a preheated hot plate and annealed at 70°C for 2 hours to obtain a 2.0 cm × 1.7 cm film. A layer of polydimethylsiloxane (PDMS) was spin-coated on the surface of the film to ensure the mechanical stability of the film and avoid short circuits in the device. Copper tape was adhered to the surface of the film as a top electrode. Two wires were soldered to the surfaces of the top and bottom electrodes, respectively. Finally, the entire device was encapsulated with polyimide tape to prepare a polycrystalline film piezoelectric device.
[0066] A clicker was used to apply a mechanical stress of about 2N at a frequency of 5Hz to the polycrystalline film piezoelectric device, and an oscilloscope was connected to record the voltage signal generated. The results are as follows: Figure 5 As shown. Figure 5 It can be seen that the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention has a strong piezoelectric signal. In addition, an ultrasonic signal generator receiver is used to drive a 10MHz ultrasonic probe, which is applied to the above-mentioned piezoelectric device, and an oscilloscope is used to display the ultrasonic signal detected by the device. The ultrasonic signals detected by the ultrasonic probe and the polycrystalline film piezoelectric device at different distances are shown in FIG. Figure 6 As shown. Figure 6 It can be seen that the polycrystalline film piezoelectric device prepared by using the chiral hybrid perovskite piezoelectric crystal material prepared by the present invention can well detect ultrasonic signals.
[0067] In summary, the present invention uses a chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride as a ligand and, through organic-inorganic hybridization with rubidium iodide, prepares a non-centrosymmetric chiral hybrid perovskite piezoelectric crystal. The present invention effectively improves the piezoelectric properties of the piezoelectric crystal material while also increasing the thermal stability of the material. The present invention uses a chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride as a ligand to prepare an organic-inorganic hybrid perovskite piezoelectric crystal material without adding any toxic metals, thus preventing environmental pollution. Furthermore, the preparation method of the present invention is simple, and the synthesis process does not consume high energy.
[0068] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.
Claims
1. A chiral hybrid perovskite piezoelectric crystal material, characterized in that: The chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride and rubidium iodide are prepared by organic-inorganic hybridization. In the chiral hybrid perovskite piezoelectric crystal material, any Rb + The ion and the six adjacent iodide ions coordinate to form an octahedron, and the octahedra form a perovskite framework by sharing corners, and the cavity of the perovskite framework is occupied by the (R)-(+)-3-aminoquinuclidine cation; The chiral organic-inorganic hybrid perovskite piezoelectric crystal material is non-centrosymmetric, its space group is P3121, and the crystal cell parameters are: α=90°, β=120°, γ=90°.
2. A method for preparing the chiral hybrid perovskite piezoelectric crystal material according to claim 1, comprising the following steps: Chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride is used as a ligand, rubidium iodide is used as a raw material, and they are mixed with a hydroiodic acid aqueous solution. The chiral organic-inorganic hybrid perovskite piezoelectric crystal material is obtained by a room temperature solvent evaporation method.
3. The preparation method according to claim 2, characterized in that The molar ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to rubidium iodide is 1:1-2.
4. The preparation method according to claim 2, characterized in that After mixing, hypophosphorous acid is added, and the usage ratio of rubidium iodide to hypophosphorous acid is 1 mol: 0.3 mL to 0.6 mL.
5. The preparation method according to claim 2, characterized in that The concentration of the hydroiodic acid aqueous solution is 0.56 g / mL to 0.85 g / mL, and the usage ratio of the chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride to the hydroiodic acid aqueous solution is 1 mol:2 mL.
6. The preparation method according to claim 2, characterized in that Chiral organic amine (R)-(+)-3-aminoquinuclidine dihydrochloride is added to a rubidium iodide aqueous solution, and then a hydroiodic acid aqueous solution is added, and ultrasonication is performed at room temperature to remove the solvent to obtain a chiral organic-inorganic hybrid perovskite piezoelectric crystal material.
7. The preparation method according to claim 6, characterized in that The solvent removal step comprises: standing at room temperature for 4 to 5 days.
8. Use of the chiral hybrid perovskite piezoelectric crystal material according to claim 1 in a piezoelectric device.