A phase-change organic-inorganic hybrid metal halide piezoelectric material and a method for preparing the same
Organic-inorganic hybrid metal halide piezoelectric materials were synthesized at room temperature via solvent evaporation and antisolvent methods, solving the environmental pollution and energy consumption problems caused by high-temperature synthesis and realizing the preparation of efficient and low-cost organic-inorganic hybrid piezoelectric materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANKAI UNIV
- Filing Date
- 2022-12-13
- Publication Date
- 2026-06-19
AI Technical Summary
Existing piezoelectric materials suffer from problems such as high energy consumption during high-temperature synthesis, serious environmental pollution, high synthesis temperature, and poor thermal stability of products during synthesis, making it difficult to synthesize environmentally friendly organic-inorganic hybrid piezoelectric materials at low temperatures.
Organic-inorganic hybrid metal halide piezoelectric materials were synthesized at room temperature using solvent evaporation and antisolvent methods. Ferric tribromide and methyltriphenylphosphine bromide were used as raw materials. Single crystals and powders of C19H18PBr4Fe were prepared by room temperature evaporation and antisolvent methods, which simplified the synthesis process and reduced energy consumption.
This method enables the efficient synthesis of high-purity, thermally stable organic-inorganic hybrid piezoelectric materials at room temperature, simplifying the operation process, reducing environmental pollution and synthesis costs, and making it suitable for mass production.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional hybrid materials technology, and relates to an organic-inorganic hybrid metal halide piezoelectric material with phase change and its preparation method. Background Technology
[0002] Energy conversion and harvesting have always played a vital role in human life and daily production. Compared with other materials, piezoelectric materials have higher mechanical energy-to-electrical energy conversion efficiency due to their more direct signal acquisition method. When a piezoelectric material is deformed under external force, its two surfaces generate charges of opposite signs. This effect is called the piezoelectric effect. Materials with the piezoelectric effect can be used as sensors to realize the conversion between electrical and mechanical stress. [1]
[0003] Piezoelectric materials are classified into inorganic piezoelectric materials, polymeric piezoelectric materials, and organic-inorganic hybrid piezoelectric materials. Inorganic piezoelectric materials, such as lead zirconate titanate (PZT), are widely used due to their excellent piezoelectric properties. However, PZT and other inorganic piezoelectric materials often contain toxic lead or heavy metals, which can cause serious environmental pollution. Furthermore, inorganic materials have low fracture toughness, and their synthesis process requires high temperatures and consumes a lot of energy. [2] Organic polymer materials have attracted widespread attention due to their excellent flexibility. Polyvinylidene fluoride (PVDF) and other materials have become candidate materials for medical sensors due to their low processing cost and excellent flexibility. However, the synthesis technology of ferroelectric PVDF is still immature. On the other hand, most pure polymers have poor piezoelectric sensitivity, making it difficult to distinguish signals from noise, thus hindering their practical application. [3] Organic-inorganic hybrid piezoelectric materials, with their simple synthesis, low synthesis temperature, high thermal stability, and strong mechanical flexibility, have become emerging materials for piezoelectric sensing and energy harvesting. [4]
[0004] Therefore, there is an urgent need for new energy harvesting materials that are environmentally friendly (free of lead and heavy metals) and do not require high-temperature synthesis processes. In summary, the primary challenge facing the field of energy conversion and harvesting materials is to synthesize novel non-centrosymmetric organic-inorganic hybrid piezoelectric materials at relatively low temperatures by selecting suitable organic ligands and metals.
[0005] References:
[0006] [1] Zhang Y, Song XJ, Zhang ZX, et al. Piezoelectric energy harvesting based on multiaxial ferroelectrics by precise molecular design [J]. Matter, 2020, 2(3): 697-710.
[0007] [2]Vijayakanth T,Liptrot DJ,Gazit E,et al.Recent Advances in Organicand Organic–Inorganic Hybrid Materials for Piezoelectric Mechanical EnergyHarvesting[J].Advanced Functional Materials,2022,32(17):2109492.
[0008] [3]Li J, Wang X. Research Update: Materials design of implantable nanogenerators for biomechanical energy harvesting[J]. APL materials, 2017, 5(7):073801.
[0009] [4]Harada J.Plastic / ferroelectric molecular crystals:Ferroelectricperformance in bulk polycrystalline forms[J].APL materials,2021,9(2):020901. Summary of the Invention
[0010] To address existing challenges, the present invention aims to provide a method for efficiently synthesizing an organic-inorganic hybrid metal halide piezoelectric material with phase change at room temperature. By selecting organophosphine ligands and ferric tribromide, and using solvent evaporation and antisolvent methods, the invention solves many problems such as complex synthesis processes, high synthesis temperatures, high energy consumption, poor thermal stability of products, high toxicity of products, and environmental pollution.
[0011] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0012] A method for synthesizing organic-inorganic hybrid metal halide piezoelectric materials with phase transition is as follows:
[0013] Solvent evaporation for single crystal preparation: Ferric tribromide and methyltriphenylphosphine bromide (C...) 19 H 18 P Br) and the reaction solvent were added to the reaction vessel, mixed thoroughly, and allowed to stand for a certain period of time to evaporate the solvent. The resulting product was then filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe crystals.
[0014] Antisolvent preparation of powder: Ferric tribromide and methyltriphenylphosphine bromide (C 19 H 18 PBr and the reaction solvent were added to the reaction vessel and mixed thoroughly. The mixture was then dropped into a container containing the antisolvent. The resulting product was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
[0015] In both of the above preparation methods, the reaction solvent is selected from one or more of anhydrous ethanol, distilled water, methanol, acetonitrile, ethyl acetate, dichloromethane, and N,N-dimethylformamide, with anhydrous ethanol and distilled water being preferred.
[0016] In the two preparation methods above, the antisolvent is selected from one or more of isopropanol, toluene, and petroleum ether, with isopropanol being preferred.
[0017] In both of the above preparation methods, the molar ratio of reactants to solvent is: C 19 H 18 PBr: Ferric tribromide: Solvent = 1:1~50:1~50000, the preferred molar ratio of reactant to solvent is: Methyltriphenylphosphine bromide: Ferric tribromide: Solvent = 1:1~1.5:500~2000. Methyltriphenylphosphine bromide (C 19 H 18 The molar ratio of PBr to ferric tribromide is 1:1 to 1:4, preferably 1:1 to 1:1.5.
[0018] In both of the above preparation methods, the reaction temperature is 10–200℃, preferably room temperature (20–30℃); the reaction time is 1–240 h, wherein the reaction time for single crystal preparation is preferably 96–120 h, and the reaction time for powder preparation is preferably 1–2 h.
[0019] In both of the above preparation methods, the solvent used for sample washing is selected from isopropanol, toluene, and petroleum ether. Isopropanol is preferred.
[0020] In the above preparation methods, the reaction vessel includes, but is not limited to, beakers, test tubes, and conical flasks, with beakers being preferred. The mixing method includes, but is not limited to, stirring and sonication, with sonication being preferred.
[0021] In the above preparation method, the drying temperature is 50-100℃, preferably 50℃, and the drying time is 1-48h, preferably 2-5h.
[0022] Compared with the prior art, the beneficial effects of the present invention are: the present invention uses two methods, room temperature evaporation and anti-solvent, to prepare C. 19 H 18 The preparation methods for single crystals and powders of PBr4Fe are simple and efficient, with a straightforward operation process that does not require high temperatures during the reaction. The synthesis cost is low, and the target product has high purity. These methods can be used for the mass production of novel organic-inorganic hybrid piezoelectric materials with high thermal stability and low environmental pollution. Attached Figure Description
[0023] Figure 1 It is C 19 H 18 Crystal structure diagram of PBr4Fe at 150K;
[0024] Figure 2 It is C 19 H 18 PXRD pattern of PBr4Fe;
[0025] Figure 3 It is C 19 H 18 Thermogravimetric diagram of PBr4Fe;
[0026] Figure 4 It is C 19 H 18 DSC image of PBr4Fe;
[0027] Figure 5 It is C 19 H 18 Crystal structure diagram of PBr4Fe at 300K;
[0028] Figure 6 It is C 19 H 18 Powder piezoelectric devices based on PBr4Fe;
[0029] Figure 7 It is C 19 H 18 Open-circuit voltage of PBr4Fe powder devices;
[0030] Figure 8 It is C 19 H 18 Short-circuit current of PBr4Fe powder devices; Detailed Implementation
[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0032] Example 1
[0033] Solution A was prepared by dissolving 0.14778 g (0.5 mmol) of ferric tribromide in 4 mL of distilled water, and solution B was prepared by dissolving 0.1786 g (0.5 mmol) of methyltriphenylphosphine bromide in 4 mL of anhydrous ethanol. Solutions A and B were mixed in a beaker and sonicated to obtain solution C. The solvent was allowed to evaporate at room temperature for 3-4 days, resulting in reddish-brown blocky crystals. The obtained product was then filtered, washed, and dried in an oven to obtain solution C. 19 H 18 PBr4Fe crystals.
[0034] Figure 1 The figure shows the single-crystal analytical structure at 150K corresponding to Example 1. As can be seen from the figure, the prepared C 19 H 18 PBr4Fe exhibits good crystallinity, indicating that the unit cell of the obtained product contains [FeBr4]. + The tetrahedrons are independent of each other and not connected. 19 H 18 PBr4Fe is a zero-dimensional organic-inorganic hybrid metal halide.
[0035] Figure 5 The figure shows the single-crystal analytical structure diagram at 300K corresponding to Example 1. As can be seen from the figure, at 300K, C 19 H 18 PBr4Fe still has good crystallinity, C 19 H 18 PBr4Fe is a zero-dimensional organic-inorganic hybrid metal halide.
[0036] Through the ZJ-3AN type quasi-static d 33 The measuring instrument measures the single-crystal piezoelectric properties d obtained in this embodiment. 33 Test, will C 19 H 18 With the PBr4Fe single crystal sandwiched between the upper and lower probes of the measuring head, and the ×0.1 resolution setting selected, the d value was measured. 33 The value is 5.6 pC / N.
[0037] Table 1 shows the single-crystal analytical structure data at 150K and 300K corresponding to Example 1. At 150K, C1 19 H 18The space group of PBr4Fe is P21, and the C at 300 K is... 19 H 18 The space group for PBr4Fe is P212121.
[0038] Table 1
[0039]
[0040] Example 2
[0041] Solution A was prepared by dissolving 0.14778 g (0.5 mmol) of ferric tribromide in 4 mL of distilled water, and solution B was prepared by dissolving 0.1786 g (0.5 mmol) of methyltriphenylphosphine bromide in 4 mL of anhydrous ethanol. Solutions A and B were mixed in a beaker and sonicated to obtain solution C. Solution C was then added dropwise to a beaker containing isopropanol. The precipitated powder was filtered, washed, and dried in an oven to obtain solution C. 19 H 18 PBr4Fe powder.
[0042] Figure 2 The image shows the PXRD pattern corresponding to Example 2. Example 2 was characterized using XRD powder diffraction at a maximum voltage of 40 kV. The instrument was turned on, and then the MiniFlexGuidance software was opened for aging. The ground powder sample was placed on a clean silicon wafer, spread and compacted, and the "Door Lock" button was pressed. After two beeps, the chamber door opened, the silicon wafer containing the sample was placed, the chamber door was closed, and the "Door Lock" button was pressed again. The test conditions were set: scan rate of 2 decibels / min, and 2θ of 3-50°. Figure 2 As can be seen, the XRD pattern of the crystal is almost identical to the theoretical calculation, indicating that the obtained crystal has high purity and confirming the high purity of C. 19 H 18 Successful synthesis of PBr4Fe.
[0043] Figure 3 The thermogravimetric analysis (TGA) chart corresponds to Example 2. The temperature range is 25-800.00℃, and the scan rate is 10℃ / min. The results are as follows: Figure 3 As shown in the figure, it is quite obvious that C 19 H 18 PBr4Fe exhibits excellent thermal stability.
[0044] Figure 4 This is the DSC diagram corresponding to Example 2. As can be seen from the diagram, C... 19 H 18 PBr4Fe undergoes a phase transition at 4℃. As the temperature increases, the concentration of PBr4Fe decreases at the phase transition temperature. 19 H 18PBr4Fe transforms from a ferroelectric phase to a paraelectric phase; as the temperature decreases, the phase transition temperature C... 19 H 18 PBr4Fe transforms from a paraelectric phase to a ferroelectric phase. This property allows C to... 19 H 18 PBr4Fe holds promise for applications in fields such as information storage and sensing monitoring.
[0045] Example 3
[0046] The C prepared in Example 2 19 H 18 A suitable amount of PBr4Fe powder sample was taken, and conductive tape was adhered to both the upper and lower surfaces. The sample was then encapsulated with PDMS / Kapton tape to create a simple sandwich-structure piezoelectric device. An appropriate amount of antistatic spray was then sprayed onto the device surface to eliminate the effects of tribostatic discharge. The resulting C... 19 H 18 PBr4Fe powder piezoelectric devices are shown in the attached figure. Figure 6 As shown.
[0047] Figure 7 For the open-circuit voltage corresponding to Example 3, a mechanical stress of 1N was applied to it using a clicker, and the resulting voltage signal was observed and recorded using an oscilloscope. As shown in the figure, C... 19 H 18 PBr4Fe powder piezoelectric devices can generate an open-circuit voltage signal of 2 to 3V under the action of force.
[0048] Figure 8 For the short-circuit current corresponding to Example 3, a mechanical stress of 1N was applied to it using a clicker, and the resulting current signal was observed and recorded using an oscilloscope. As shown in the figure, C... 19 H 18 PBr4Fe powder piezoelectric devices can generate a short-circuit current signal of 0.3 to 0.4 μA under force.
[0049] Example 4
[0050] 1.4778 g (5 mmol) of ferric tribromide and 1.786 g (5 mmol) of methyltriphenylphosphine bromide were dissolved in 30 mL of anhydrous ethanol and mixed thoroughly. The mixture was then added dropwise to a beaker containing isopropanol. The precipitated powder was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
[0051] Example 5
[0052] 1.4778 g (5 mmol) of ferric tribromide and 1.786 g (5 mmol) of methyltriphenylphosphine bromide were dissolved in 30 mL of distilled water and mixed thoroughly. The mixture was then added dropwise to a beaker containing isopropanol. The precipitated powder was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
[0053] Example 6
[0054] 2.9556 g (10 mmol) of ferric tribromide and 1.786 g (5 mmol) of methyltriphenylphosphine bromide were dissolved in 50 mL of anhydrous ethanol and mixed thoroughly. The mixture was then added dropwise to a beaker containing petroleum ether. The precipitated powder was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
[0055] Example 7
[0056] 1.4778 g (5 mmol) of ferric tribromide and 1.786 g (5 mmol) of methyltriphenylphosphine bromide were dissolved in 50 mL of acetonitrile and mixed thoroughly. The mixture was then added dropwise to a beaker containing isopropanol. The precipitated powder was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
[0057] Example 8
[0058] 14.778 g (5 mol) of ferric tribromide and 17.86 g (5 mol) of methyltriphenylphosphine bromide were dissolved in 200 mL of N,N-dimethylformamide and mixed thoroughly. The mixture was then added dropwise to a beaker containing toluene. The precipitated powder was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
[0059] This invention provides a method for the efficient synthesis of an organic-inorganic hybrid metal halide piezoelectric material with phase change at room temperature. It utilizes a combination of methyltriphenylphosphine bromide and ferric tribromide, employing solvent evaporation and antisolvent methods to address numerous problems associated with current synthesis processes, such as complex processes, high synthesis temperatures, high energy consumption, poor thermal stability of the product, high product toxicity, and environmental pollution. This invention uses both room-temperature evaporation and antisolvent methods to prepare C... 19 H 18 The preparation methods for single crystals and powders of PBr4Fe are simple and efficient, with a straightforward operation process that does not require high temperatures during the reaction. The synthesis cost is low, and the target product has high purity. These methods can be used for the mass production of novel organic-inorganic hybrid piezoelectric materials with high thermal stability and low environmental pollution.
[0060] The above description of the embodiments is provided to enable those skilled in the art to understand and apply the present invention. Those skilled in the art can readily make various modifications to these embodiments, including but not limited to modifying the solvent used, the ratio of reaction ligands, the solvent ratio, the reaction time, and the temperature, and applying the general principles described herein to other embodiments without inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the protection scope of the present invention.
Claims
1. An organic-inorganic hybrid metal halide piezoelectric material having a phase transition, characterized in that, The organic-inorganic hybrid metal halide piezoelectric material has the chemical formula C. 19 H 18 PBr4Fe is a piezoelectric crystal with phase transition synthesized using organophosphorus ligands as raw materials. The organophosphorus ligand is named methyltriphenylphosphine bromide, and its chemical formula is C1. 19 H 18 PBr, an organic-inorganic hybrid metal halide piezoelectric material, can generate piezoelectric signals under the action of force.
2. The organic-inorganic hybrid metal halide piezoelectric material with phase change according to claim 1, characterized in that, The phase-change organic-inorganic hybrid metal halide piezoelectric material is a non-centrosymmetric, zero-dimensional bulk crystal, the space group of which is P21, and the crystal cell parameter of which is: α = 90°, β = 91.083(1)°, γ = 90°.
3. A method for producing the phase-transition organic-inorganic hybrid metal halide piezoelectric material according to claim 1 or 2, characterized by, The preparation method is as follows: A, solvent evaporation to produce C 19 H 18 Br4FeP single crystal Ferric tribromide and methyltriphenylphosphine bromide (C 19 H 18 PBr) and the reaction solvent were added to the reaction vessel, mixed thoroughly, and allowed to stand for a certain period of time to evaporate the solvent. The resulting product was then filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe crystals; B, anti-solvent preparation C 19 H 18 Br4FeP powder Ferric tribromide and methyltriphenylphosphine bromide (C 19 H 18 PBr and the reaction solvent were added to the reaction vessel and mixed thoroughly. The mixture was then dropped into a container containing the antisolvent. The resulting product was filtered, washed, and dried in an oven to obtain C. 19 H 18 PBr4Fe powder.
4. The method of claim 3, wherein the method is characterized by: C 19 H 18 In the two methods for preparing PBr4Fe, the reaction solvent includes, but is not limited to, one or more of anhydrous ethanol, distilled water, methanol, acetonitrile, ethyl acetate, dichloromethane, and N,N-dimethylformamide; the antisolvent includes, but is not limited to, one or more of isopropanol, toluene, and petroleum ether; the reaction vessel includes, but is not limited to, beakers, test tubes, and conical flasks; and the mixing method includes, but is not limited to, stirring and sonication.
5. The method of claim 3, wherein the method is characterized by: C 19 H 18 In the two methods for preparing PBr4Fe, the molar ratio of reactants to solvent is: C 19 H 18 PBr: Ferric tribromide: Solvent = 1:1~50:1~50000, where C 19 H 18 The molar ratio of PBr to ferric tribromide is 1:1 to 1:4; the reaction temperature is 10 to 200℃; and the reaction time is 1 to 240 h.
6. The method for preparing an organic-inorganic hybrid metal halide piezoelectric material with phase change according to claim 3, characterized in that, The organic-inorganic hybrid metal halide piezoelectric material exhibits a reversible phase transition during heating and cooling.
7. Use of a phase-transition organic-inorganic hybrid metal halide piezoelectric material according to claim 1 or 2, characterized in that, This material has piezoelectric output properties and can be applied to energy conversion and energy harvesting.
8. Use of a phase-change organic-inorganic hybrid metal halide piezoelectric material according to claim 7, characterized in that, The material piezoelectric constant d 33 is 5.6 pC / N.
9. Use of a phase-change organic-inorganic hybrid metal halide piezoelectric material according to claim 7, characterized in that, When a force of 1 N is applied to a piezoelectric device, the open-circuit voltage of this material is 2 to 3 V.
10. Use of a phase-change organic-inorganic hybrid metal halide piezoelectric material according to claim 7, characterized in that, When a force of 1 N is applied to a piezoelectric device, the short-circuit current of this material is 0.3 to 0.4 μA.