An organic-inorganic hybrid perovskite phase change material and its preparation method and application

Abstract

This application, applicable to the field of materials technology, provides an organic-inorganic hybrid perovskite phase change material, its preparation method, and application. The structural formula of the organic-inorganic hybrid perovskite phase change material is: #imgabs0#. This application uses an H / X substitution strategy to adjust the 4-fluoro-3-nitroaniline organic ligand, achieving effective regulation of the internal structure of the organic-inorganic hybrid perovskite material, resulting in high thermal stability and semiconductor properties. In addition, the organic-inorganic hybrid perovskite phase change material of this application can be prepared at room temperature, using a simple operation method that does not require complex instrumentation, does not contain any harmful ingredients, and is very environmentally friendly.

Description

Technical Field

[0001] The present application belongs to the field of material technology, and in particular relates to an organic-inorganic hybrid perovskite phase change material and a preparation method and application thereof. Background Art

[0002] Perovskite materials, due to their remarkable performance advantages, have been widely used in a variety of fields, including solar cells, light-emitting diodes, lasers, and photodetectors. A prominent property is their phase transition, which means that the material's crystal structure undergoes transformations under different temperature or pressure conditions. This phase transition not only affects the material's physical properties, such as band gap, carrier mobility, and light absorption coefficient, but may also affect its chemical stability. Although researchers are exploring various strategies to design perovskite materials with specific functionalities, the phase transition characteristics of perovskite materials remain challenging for practical applications. For example, in solar cells, temperature fluctuations can cause phase instabilities in the material, further affecting device efficiency and lifetime. Therefore, the development of stable perovskite materials that can withstand environmental changes has become a key research direction. Compared to the simple and rigid structures of traditional inorganic perovskites, organic-inorganic hybrid perovskites exhibit remarkable structural diversity and tunable physical properties. The versatility of these materials and their stability under varying temperatures open up new prospects for applications in extreme environments.

[0003] Traditional inorganic perovskite materials usually need to be synthesized under high temperature conditions, which leads to high production costs and poor material flexibility. In addition, most of these materials contain lead components that are harmful to the environment, which severely limits their application areas. In contrast, organic-inorganic hybrid perovskite materials combine the advantages of organic and inorganic materials, are simple to process, easy to synthesize, have non-toxic components, have high flexibility and a wide range of mechanical properties, and are expected to overcome many of the defects of traditional inorganic perovskite materials. Therefore, the development of stable organic-inorganic hybrid perovskite phase change materials has become a key direction of current research. Summary of the Invention

[0004] The purpose of the embodiments of the present application is to provide an organic-inorganic hybrid perovskite phase change material, aiming to develop an organic-inorganic hybrid perovskite material with a higher phase transition temperature.

[0005] The embodiment of the present application is implemented as follows: an organic-inorganic hybrid perovskite phase change material, the structural formula of the organic-inorganic hybrid perovskite phase change material is:

[0006]

[0007] Another object of the embodiments of the present application is a method for preparing the above-mentioned organic-inorganic hybrid perovskite phase change material, comprising:

[0008] 4-Fluoro-3-nitroaniline, 18-crown-6 and ferric chloride are dissolved in methanol and dilute hydrochloric acid, filtered and evaporated to obtain an organic-inorganic hybrid perovskite phase change material;

[0009] The molar ratio of the 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride is 1:1:1.

[0010] Another purpose of an embodiment of the present application is to apply the above-mentioned organic-inorganic hybrid perovskite phase change material in the field of thermal energy storage and temperature control.

[0011] The present invention provides an organic-inorganic hybrid perovskite phase-change material. By employing an H / X substitution strategy to adjust the 4-fluoro-3-nitroaniline organic ligand, the material's internal structure is effectively controlled, resulting in high thermal stability and semiconductor properties. Furthermore, the organic-inorganic hybrid perovskite phase-change material can be prepared at room temperature using a simple process that does not require complex instrumentation and equipment. Furthermore, the material contains no harmful ingredients and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 A flow chart for preparing the organic-inorganic hybrid perovskite phase change material provided in the embodiments of the present application;

[0013] Figure 2 A unit cell structure diagram of the organic-inorganic hybrid perovskite phase change material provided in an embodiment of the present application;

[0014] Figure 3 The UV-visible absorption spectrum of the organic-inorganic hybrid perovskite phase change material provided in the embodiments of the present application;

[0015] Figure 4 This is the DSC spectrum of the organic-inorganic hybrid perovskite phase change material provided in the examples of the present application. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical solutions and advantages of this application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0017] The present invention provides an organic-inorganic hybrid perovskite phase change material. The structural formula of the organic-inorganic hybrid perovskite phase change material is as follows:

[0018]

[0019] by Figure 1As an example, the present embodiment further provides a method for preparing the above-mentioned organic-inorganic hybrid perovskite phase change material, comprising:

[0020] 4-Fluoro-3-nitroaniline, 18-crown-6 and ferric chloride are dissolved in methanol and dilute hydrochloric acid, filtered and volatilized to obtain an organic-inorganic hybrid perovskite phase change material.

[0021] The molar ratio of 4-fluoro-3-nitroaniline, 18-crown-6, and ferric chloride is 1:1:1. During the early research and development process, this application tried experiments with the input ratios of 4-fluoro-3-nitroaniline ligand, 18-crown-6, and metal salt being 1:0:1, 1:0:2, 1:1:1, 2:0:1, 2:2:1, 1:1:2, 2:1:2, 2:1:1, 1:2:2, and 3:1:3, respectively. Only when the molar ratio of 4-fluoro-3-nitroaniline, 18-crown-6, and ferric chloride was 1:1:1, could a better crystalline organic-inorganic hybrid perovskite phase change material be obtained.

[0022] The ferric chloride is ferric chloride hexahydrate. Regarding metal ions, during the early stages of research and development, this application tested ferric chloride, cadmium chloride, copper chloride, manganese chloride, zinc chloride, cobalt chloride, lead chloride, lead bromide, cobalt bromide, cadmium bromide, and zinc bromide. Only when the metal ion was iron could a better crystalline organic-inorganic hybrid perovskite phase change material be obtained.

[0023] Among them, the solvent used in this application is methanol. During the early research and development process, this application tried solvents such as water, methanol, ethanol, acetonitrile, acetone, DMF, dichloromethane, etc. Only when the solvent is methanol can a better crystal form of organic-inorganic hybrid perovskite phase change material be obtained.

[0024] Among them, in the step of dissolving 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride hexahydrate with methanol and dilute hydrochloric acid, filtering and volatilizing to obtain the organic-inorganic hybrid perovskite phase change material, the temperature is controlled at 25-80°C, preferably room temperature.

[0025] The step of dissolving 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride with methanol and dilute hydrochloric acid, filtering and volatilizing to obtain an organic-inorganic hybrid perovskite phase change material comprises:

[0026] 4-Fluoro-3-nitroaniline, 18-crown-6 and ferric chloride are placed in a beaker containing an appropriate amount of methanol, and excess dilute hydrochloric acid is added thereto for stirring and dissolution. After filtering to remove insoluble impurities, the resulting solution is placed in a crystal culture dish and kept still for volatilization to obtain an organic-inorganic hybrid perovskite phase change material.

[0027] Alternatively, 10 mmol, 1.56 g, of 4-fluoro-3-nitroaniline, 10 mmol, 2.64 g, of 18-crown-6, and 10 mmol, 2.70 g, of ferric chloride hexahydrate, are placed in a container containing methanol. 1.30 g of dilute hydrochloric acid is added dropwise, stirred to dissolve, and insoluble impurities are removed by filtration. The resulting solution is placed in a crystal culture dish and allowed to stand at room temperature. Yellow block crystals are obtained by slow evaporation. The resulting precursor solution is then spin-coated onto an ITO glass substrate, and a thin film is obtained using a spin coater.

[0028] The following examples describe organic-inorganic hybrid perovskite phase change materials, their preparation methods, and applications in detail. The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials and reagents used are commercially available unless otherwise specified.

[0029] Example: Preparation of organic-inorganic hybrid perovskite phase change material [(C6H7N2O2F)(18-crown-6)][FeCl4], the synthesis route of which is shown below:

[0030]

[0031] Accurately weigh 4-fluoro-3-nitroaniline (10mmol, 1.56g), 18-crown-6 (10mmol, 2.64g) and ferric chloride hexahydrate (10mmol, 2.70g) and place them in a beaker containing an appropriate amount of methanol. Add 1.30g of dilute hydrochloric acid (excess) dropwise thereto, stir to dissolve, filter to remove insoluble impurities, and obtain a clear and transparent solution. The resulting solution is placed in a crystal culture dish and kept at room temperature. Yellow block crystals (compound 2) are obtained by slow evaporation. The resulting precursor solution is then spin-coated on an ITO glass substrate and a thin film is obtained using a spin coater. The unit cell structure of compound 2 is as follows: Figure 2 shown.

[0032] The organic-inorganic hybrid perovskite phase change material prepared in the examples of this application has high thermal stability and semiconductor properties. According to differential scanning calorimetry testing, the organic-inorganic hybrid perovskite phase change material undergoes a first-order reversible phase transition at 381K.

[0033] Test Example 1: UV-Vis Absorption Spectrum Test

[0034] Ultraviolet-visible spectroscopy is an important method for studying the semiconductor properties of organic-inorganic hybrid perovskite materials. Through UV-visible spectroscopy, the material's absorption of light of different wavelengths can be determined, thereby inferring the material's band structure and optical band gap. To determine the semiconductor properties of the organic-inorganic hybrid perovskite phase-change material prepared in the above examples, this application conducted UV-visible absorption spectroscopy within the range of 200-800 nm and obtained its absorption spectrum.

[0035] The absorption spectrum of the organic-inorganic hybrid perovskite phase change material prepared in the embodiment of the present application is as follows: Figure 3 As shown, it gradually shows an absorption edge at around 479 nm. According to the Tauc curve, its spectral band gap Eg is 2.2587 eV, indicating that it has semiconductor properties and is a potential semiconductor material.

[0036] Test Example 2: Study on the Phase Change Process of Organic-Inorganic Hybrid Perovskite Phase Change Materials

[0037] The phase transition properties of organic-inorganic hybrid perovskite materials are one of the key factors affecting their application performance. To gain a deeper understanding of this property, differential scanning calorimetry (DSC) can be used to analyze the thermodynamic behavior of the material and determine whether the compound exhibits a temperature-dependent reversible structural phase transition.

[0038] The DSC spectrum of the organic-inorganic hybrid perovskite phase change material prepared in the above embodiment is as follows: Figure 4 As shown in the figure, a pair of endothermic / exothermic peaks were observed at 108°C / 38°C, with a thermal hysteresis of 70K. The sharp peak shape and large thermal hysteresis indicate that the organic-inorganic hybrid perovskite phase change material has undergone a discontinuous first-order reversible phase transition. This result indicates that the organic-inorganic hybrid perovskite phase change material can be used as a potential phase change material in fields such as thermal energy storage and temperature control.

[0039] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0040] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. An organic-inorganic hybrid perovskite phase change material, characterized in that: The structural formula of the organic-inorganic hybrid perovskite phase change material is: The preparation method of the organic-inorganic hybrid perovskite phase change material comprises: 4-Fluoro-3-nitroaniline, 18-crown-6 and ferric chloride are dissolved in methanol and dilute hydrochloric acid, filtered and evaporated to obtain an organic-inorganic hybrid perovskite phase change material; The molar ratio of 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride is 1:1:1; In the step of dissolving 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride with methanol and dilute hydrochloric acid, filtering and volatilizing to obtain the organic-inorganic hybrid perovskite phase change material, the temperature is controlled at 25-80°C.

2. A method for preparing the organic-inorganic hybrid perovskite phase change material according to claim 1, characterized in that: include: 4-Fluoro-3-nitroaniline, 18-crown-6 and ferric chloride are dissolved in methanol and dilute hydrochloric acid, filtered and evaporated to obtain an organic-inorganic hybrid perovskite phase change material; The molar ratio of 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride is 1:1:1; In the step of dissolving 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride with methanol and dilute hydrochloric acid, filtering and volatilizing to obtain the organic-inorganic hybrid perovskite phase change material, the temperature is controlled at 25-80°C.

3. The method for preparing the organic-inorganic hybrid perovskite phase change material according to claim 2, wherein the temperature is controlled to be room temperature.

4. The method for preparing the organic-inorganic hybrid perovskite phase change material according to claim 2, characterized in that: The ferric chloride is ferric chloride hexahydrate.

5. The method for preparing the organic-inorganic hybrid perovskite phase change material according to claim 2, characterized in that: The step of dissolving 4-fluoro-3-nitroaniline, 18-crown-6 and ferric chloride with methanol and dilute hydrochloric acid, filtering and volatilizing to obtain the organic-inorganic hybrid perovskite phase change material comprises: 4-Fluoro-3-nitroaniline, 18-crown-6 and ferric chloride are placed in a beaker containing an appropriate amount of methanol, and excess dilute hydrochloric acid is added thereto for stirring and dissolution. After filtering to remove insoluble impurities, the resulting solution is placed in a crystal culture dish and kept still for volatilization to obtain an organic-inorganic hybrid perovskite phase change material.

6. The method for preparing the organic-inorganic hybrid perovskite phase change material according to claim 2, characterized in that: The organic-inorganic hybrid perovskite phase change material undergoes a first-order reversible phase transition at 381K.

7. The method for preparing the organic-inorganic hybrid perovskite phase change material according to claim 2, characterized in that: The spectral band gap Eg of the organic-inorganic hybrid perovskite phase change material is 2.2587 eV.

8. Use of the organic-inorganic hybrid perovskite phase change material according to claim 1 in the fields of thermal energy storage and temperature control.

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