Molecular perovskite energetic material spherocrystal and preparation method thereof

Abstract

The invention provides a molecular perovskite energetic material spherocrystal and a preparation method thereof, and belongs to the technical field of energetic material preparation. On one hand, the particle size of a molecular perovskite energetic material is reduced through refinement, so that the sensitivity of the molecular perovskite energetic material is reduced, and the performance of the molecular perovskite energetic material is improved; on the other hand, the spheroidized growth of the crystal is controlled through the polymer, the friction sensitivity of the molecular perovskite energetic material is further reduced, the problem of high mechanical sensitivity of the molecular perovskite energetic material is effectively solved, and effective support is provided for expanding the practical application field of the molecular perovskite energetic material.

Description

Technical Field

[0001] This invention belongs to the technical field of energetic material preparation, and specifically discloses a molecular perovskite energetic material spherulite and its preparation method. Background Technology

[0002] Energetic materials are compounds or mixtures containing explosive groups or oxidizers and combustibles that can independently undergo chemical reactions and output energy. Black powder was the world's first energetic material, composed of combustible charcoal, sulfur, and the oxidizer potassium nitrate. With the development of synthetic chemistry, fuels and oxidizers could be assembled into a single molecule, thus ushering in a new era of modern explosives. Currently, known energetic materials are mainly CHNO-type nitro compounds with -NO2 as the explosive group, such as trinitrotoluene (TNT), RDX, octogen (HMX), and hexanitrohexaazaisowulzane (CL-20). However, CHNO-type energetic materials have limitations: on the one hand, there is a limit to the crystal density (ρ). max = 2.2 g / cm 3 The energy storage and release of high-energy-density materials are nearing their limits; on the other hand, there is an inherent contradiction between energy, sensitivity, and stability—the higher the energy, the higher the sensitivity, and the worse the stability. Therefore, in order to overcome these limitations, it is urgent to research and explore the design of next-generation high-energy-density materials.

[0003] With the continuous exploration of next-generation high-energy-density materials, many types of energetic compounds have emerged in recent decades, such as nitrogen-rich compounds, all-nitrogen compounds, energetic salts, energetic metal-organic frameworks, or coordination compounds. However, most of these new energetic materials face limitations in their application prospects due to contradictions between energy, sensitivity, cost, or preparation methods, making it difficult to meet the increasingly stringent requirements of modern weapon development regarding the energy, safety, mechanical properties, and environmental adaptability of energetic materials. To address this issue, one approach is to continue synthesizing new elemental explosives; another is to continuously improve the performance of existing explosives by modifying their crystal structure and morphology, thereby enhancing and expanding their applications. However, the development of elemental explosives is currently very slow, with only a dozen or so types widely applicable. Therefore, it is essential to improve the performance of existing explosives by controlling their crystal morphology.

[0004] Molecular perovskite energetic materials are a novel type of energetic material first reported by Academician Chen Xiaoming's team in 2018. Due to their advantages such as high explosive power, high stability, and low cost, they have attracted widespread attention in the field of explosives and pyrotechnics since their inception. Among them, the ammonium perchlorate-based molecular perovskite energetic material (H2dabco)[NH4(ClO4)3] (DAP-4) is currently a research hotspot due to its excellent detonation characteristics comparable to the existing high-energy explosive HMX and its good thermal stability. A few domestic explosives and pyrotechnics related units have conducted initial explorations in the performance evaluation and optimization of molecular perovskite energetic materials and their application research. The measured detonation velocity of DAP-4 can reach 8.5 km / s, the measured heat of explosion is 5.69 MJ / kg, and the theoretically calculated detonation pressure reaches 35.2 GPa. Its thermal decomposition temperature can reach 400 ℃, and its initial thermal decomposition temperature is as high as 360 ℃. It has undergone a stability evaluation by the China Ordnance 204 Institute, the only professional research institute in China specializing in pyrotechnics technology, and remains stable even at 250 ℃ for 170 hours, outperforming similar high-energy explosives. However, its high mechanical sensitivity significantly limits its practical application in modern weaponry. Summary of the Invention

[0005] This invention provides a method for preparing spherulites of molecular perovskite energetic materials using crystal control technology. The method of this invention can obtain highly spherical molecular perovskite energetic materials, and the excellent properties of spherical energetic materials effectively solve the problem of high mechanical sensitivity of molecular perovskite energetic materials.

[0006] This invention provides a method for preparing molecular perovskite energetic material spherulites, comprising the following steps: S1, based on the solubility of the molecular perovskite energetic material in the solvent at a preset temperature, calculate the mass of the molecular perovskite energetic material and the volume of the solvent required to prepare a saturated solution of the molecular perovskite energetic material; S2, with the total mass of the molecular perovskite energetic material saturated solution and crystal form regulator being 100%, the mass of the crystal form regulator is calculated according to the mass fraction of the crystal form regulator being 5~15%. The molecular perovskite energetic material and crystal form regulator are added to the solvent at a preset temperature and completely dissolved to prepare a molecular perovskite energetic material / crystal form regulator saturated solution. S3, at a volume ratio of 1:10~20, the saturated solution of molecular perovskite energetic material / crystal form regulator prepared in step S2 is added dropwise to the antisolvent at room temperature and stirred to obtain a white suspension; S4. The white suspension obtained in step S3 is filtered, washed, and dried to obtain molecular perovskite energetic material spherulites.

[0007] Preferably, the molecular perovskite energetic material is a perchlorate-based molecular perovskite energetic material.

[0008] Preferably, the molecular perovskite energetic materials are (H2dabco)[NH4(ClO4)3] (DAP-4), (H2dabco)[Na(ClO4)3] (DAP-1), (H2dabco)[K(ClO4)3] (DAP-2), (H2mpz)[NH4(ClO4)3] (PAP-M4), (H2pz)[NH4(ClO4)3] (PAP-4), (H2hpz)[NH4(ClO4)3] (PAP-H4), (H2dabco-O)[NH4(ClO4)3] (DAP-O4), (H2mdabco)[NH4(ClO4)3] (DAP-M4), (H2dabco)[NH3OH(ClO4)3] (DAP-6), and (H2dabco)[ One of the [NH2NH3(ClO4)3] (DAP-7).

[0009] Preferably, the preset temperature is 40℃-70℃.

[0010] Preferably, the solvent is one of dimethyl sulfoxide and dimethylformamide.

[0011] Preferably, the crystal form regulator is one of polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG).

[0012] Preferably, the antisolvent is one of anhydrous ethanol, ethyl acetate, or 1,2-dichloroethane.

[0013] Preferably, in step S3, the saturated solution of molecular perovskite energetic material / crystal form regulator is slowly added dropwise to the antisolvent at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate is controlled at 500 r / min.

[0014] The present invention also provides a molecular perovskite energetic material spherulite, which is prepared by the above-mentioned method for preparing molecular perovskite energetic material spherulite.

[0015] Compared with the prior art, the present invention has the following beneficial effects.

[0016] This invention provides a method for preparing spherulites of molecular perovskite energetic materials. On the one hand, by refining the particle size of the molecular perovskite energetic materials, the sensitivity of the materials is reduced, thereby improving their performance. On the other hand, by controlling the spherical growth of crystals through polymer, the friction sensitivity of the molecular perovskite energetic materials is further reduced. This effectively solves the problem of high mechanical sensitivity of molecular perovskite energetic materials and provides effective support for expanding their practical application fields. Attached Figure Description

[0017] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0018] Figure 1 This is a process flow diagram for preparing molecular perovskite spherulites according to the present invention; Figure 2 Scanning electron microscope images of raw material DAP-4 (a) and Examples 1-8 (b-i); Figure 3 X-ray diffraction patterns of DAP-4 before and after spheroidization in Example 8; Figure 4 This is a particle size distribution diagram of DAP-4 raw material; Figure 5 This is a particle size distribution diagram of DAP-4 after spheroidization in Example 8. Detailed Implementation

[0019] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 70°C, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0021] The steps are as follows: S0, Weigh 10 g of DAP-4 into a beaker, add 20 mL of dimethyl sulfoxide, and in the temperature range of 20℃-70℃, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃ for every 5℃ increase in temperature. Calculate the solubility of DAP-4 in dimethyl sulfoxide at 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, and 70℃. S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 70℃, calculate that the mass of DAP-4 required to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 50mL. S2, at 70℃, 10g of DAP-4 and 5% of PVP were added to 50 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 50 mL of anhydrous ethanol at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 spherulites, as shown. Figure 2 As shown in (b).

[0022] Example 2 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is N,N-dimethylformamide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0023] The steps are as follows: S0, Weigh 10 g of DAP-4 into a beaker, add 20 mL of N,N-dimethylformamide, and in the temperature range of 20℃-70℃, for every 10℃ increase in temperature, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃. Calculate the solubility of DAP-4 in N,N-dimethylformamide at 20℃, 30℃, 40℃, 50℃, 60℃, and 70℃. S1. Based on the solubility of DAP-4 in N,N-dimethylformamide at 40℃, calculate that the mass of DAP-4 required to prepare a saturated solution of DAP-4 is 10g and the volume of N,N-dimethylformamide is 50mL. S2, at 40℃, 10g of DAP-4 and 5% of PVP were added to 50 mL of N,N-dimethylformamide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 50 mL of anhydrous ethanol at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 crystals, as shown. Figure 2 As shown in (c).

[0024] Example 3 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is ethyl acetate, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0025] The steps are as follows: S0, same as in Example 1; S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 40℃, the required mass of DAP-4 to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of DAP-4 and 5% PVP were added to 20 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 50 mL of ethyl acetate using a peristaltic pump at a rate of 12.5 mL / min, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 crystals, as shown. Figure 2 As shown in (d).

[0026] Example 4 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is 1,2-dichloroethane, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0027] The steps are as follows: S0, same as in Example 1; S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 40℃, the required mass of DAP-4 to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of DAP-4 and 5% PVP were added to 20 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 50 mL of 1,2-dichloroethane using a peristaltic pump at a rate of 12.5 mL / min, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 crystals, as shown. Figure 2 As shown in (e).

[0028] Example 5 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:15.

[0029] The steps are as follows: S0, same as in Example 1; S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 40℃, the required mass of DAP-4 to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of DAP-4 and 5% PVP were added to 20mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 75 mL of anhydrous ethanol using a peristaltic pump at a rate of 12.5 mL / min, while controlling the stirring rate at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 spherulites, as shown. Figure 2 As shown in (f).

[0030] Example 6 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:20.

[0031] The steps are as follows: S0, same as in Example 1; S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 40℃, the required mass of DAP-4 to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of DAP-4 and 5% PVP were added to 20mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 100 mL of anhydrous ethanol at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 spherulites, as shown. Figure 2 As shown in (g).

[0032] Example 7 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 10%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:20.

[0033] The steps are as follows: S0, same as in Example 1; S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 40℃, the required mass of DAP-4 to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of DAP-4 and 10% of PVP are added to 20mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 100 mL of anhydrous ethanol at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 spherulites, as shown. Figure 2 As shown in (h).

[0034] Example 8 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 15%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:20.

[0035] The steps are as follows: S0, same as in Example 1; S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 40℃, the required mass of DAP-4 to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of DAP-4 and 15% of PVP were added to 20mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated DAP-4 / PVP solution was slowly added dropwise to 100 mL of anhydrous ethanol at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4, after stirring for another 30 minutes, filter, wash, and dry the white suspension to obtain DAP-4 spherulites, as shown. Figure 2 As shown in (i).

[0036] Example 9 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is PAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 70°C, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0037] The steps are as follows: S0, Weigh 10 g of PAP-4 into a beaker, add 20 mL of dimethyl sulfoxide, and in the temperature range of 20℃-70℃, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃ for every 5℃ increase in temperature. Calculate the solubility of PAP-4 in dimethyl sulfoxide at 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, and 70℃. S1. Based on the solubility of PAP-4 in dimethyl sulfoxide at 70℃, the required mass of PAP-4 to prepare a saturated solution of PAP-4 is 10g, and the volume of dimethyl sulfoxide is 50mL. S2, at 70℃, 10g of PAP-4 and 5% of PVP were added to 50 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated PAP-4 / PVP solution. S3. At room temperature, 5 mL of saturated PAP-4 / PVP solution was slowly added dropwise to 50 mL of anhydrous ethanol using a peristaltic pump at a rate of 12.5 mL / min, while controlling the stirring rate at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain DAP-4 spherulites.

[0038] Example 10 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is PAP-H4, the solvent is N,N-dimethylformamide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0039] The steps are as follows: S0, Weigh 10 g of PAP-H4 into a beaker, add 20 mL of N,N-dimethylformamide, and in the temperature range of 20℃-70℃, for every 10℃ increase in temperature, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃. Calculate the solubility of PAP-H4 in N,N-dimethylformamide at 20℃, 30℃, 40℃, 50℃, 60℃, and 70℃. S1. Based on the solubility of PAP-H4 in N,N-dimethylformamide at 40℃, calculate that the mass of PAP-H4 required to prepare a saturated solution of PAP-H4 is 10g and the volume of N,N-dimethylformamide is 50mL. S2, at 40℃, 10g of PAP-H4 and 5% of PVP were added to 50 mL of N,N-dimethylformamide and stirred until completely dissolved to prepare a saturated PAP-H4 / PVP solution. S3. At room temperature, 5 mL of saturated PAP-H4 / PVP solution was slowly added dropwise to 50 mL of anhydrous ethanol at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain DAP-4 crystals.

[0040] Example 11 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is PAP-M4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PVP with a mass fraction of 5%, the antisolvent is ethyl acetate, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0041] The steps are as follows: S0, Weigh 10 g of PAP-M4 into a beaker, add 20 mL of dimethyl sulfoxide, and in the temperature range of 20℃-70℃, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃ for every 5℃ increase in temperature. Calculate the solubility of PAP-M4 in dimethyl sulfoxide at 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, and 70℃. S1. Based on the solubility of PAP-M4 in dimethyl sulfoxide at 40℃, calculate that the mass of PAP-M4 required to prepare a saturated solution of PAP-M4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of PAP-M4 and 5% PVP were added to 20 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated PAP-M4 / PVP solution. S3. At room temperature, 5 mL of saturated PAP-M4 / PVP solution was slowly added dropwise to 50 mL of ethyl acetate using a peristaltic pump at a rate of 12.5 mL / min, while controlling the stirring rate at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain DAP-4 crystals.

[0042] Example 12 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is DAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 70℃, the crystal form regulator is PEG with a mass fraction of 10%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0043] The steps are as follows: S0, Weigh 10 g of DAP-4 into a beaker, add 20 mL of dimethyl sulfoxide, and in the temperature range of 20℃-70℃, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃ for every 5℃ increase in temperature. Calculate the solubility of DAP-4 in dimethyl sulfoxide at 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, and 70℃. S1. Based on the solubility of DAP-4 in dimethyl sulfoxide at 70℃, calculate that the mass of DAP-4 required to prepare a saturated solution of DAP-4 is 10g and the volume of dimethyl sulfoxide is 50mL. S2, at 70℃, 10g of DAP-4 and 10% of PEG are added to 50 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated DAP-4 / PEG solution. S3. At room temperature, 5 mL of saturated DAP-4 / PEG solution was slowly added dropwise to 50 mL of anhydrous ethanol using a peristaltic pump at a rate of 12.5 mL / min, while controlling the stirring rate at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain DAP-4 spherulites.

[0044] Example 13 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is PAP-4, the solvent is dimethyl sulfoxide, the preset temperature is 70℃, the crystal form regulator is PEG with a mass fraction of 10%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0045] The steps are as follows: S0, Weigh 10 g of PAP-4 into a beaker, add 20 mL of dimethyl sulfoxide, and in the temperature range of 20℃-70℃, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃ for every 5℃ increase in temperature. Calculate the solubility of PAP-4 in dimethyl sulfoxide at 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, and 70℃. S1. Based on the solubility of PAP-4 in dimethyl sulfoxide at 70℃, the required mass of PAP-4 to prepare a saturated solution of PAP-4 is 10g, and the volume of dimethyl sulfoxide is 50mL. S2, at 70℃, 10g of PAP-4 and 5% of PEG were added to 50 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated PAP-4 / PEG solution. S3. At room temperature, 5 mL of saturated PAP-4 / PEG solution was slowly added dropwise to 50 mL of anhydrous ethanol using a peristaltic pump at a rate of 12.5 mL / min, while controlling the stirring rate at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain PAP-4 spherulites.

[0046] Example 14 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is PAP-H4, the solvent is N,N-dimethylformamide, the preset temperature is 40℃, the crystal form regulator is PEG with a mass fraction of 10%, the antisolvent is anhydrous ethanol, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0047] The steps are as follows: S0, Weigh 10 g of PAP-H4 into a beaker, add 20 mL of N,N-dimethylformamide, and in the temperature range of 20℃-70℃, for every 10℃ increase in temperature, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃. Calculate the solubility of PAP-H4 in N,N-dimethylformamide at 20℃, 30℃, 40℃, 50℃, 60℃, and 70℃. S1. Based on the solubility of PAP-H4 in N,N-dimethylformamide at 40℃, calculate that the mass of PAP-H4 required to prepare a saturated solution of PAP-H4 is 10g and the volume of N,N-dimethylformamide is 50mL. S2, at 40℃, 10g of PAP-H4 and 5% of PEG were added to 50 mL of N,N-dimethylformamide and stirred until completely dissolved to prepare a saturated PAP-H4 / PEG solution. S3. At room temperature, 5 mL of saturated PAP-H4 / PEG solution was slowly added dropwise to 50 mL of anhydrous ethanol using a peristaltic pump at a rate of 12.5 mL / min, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain PAP-H4 crystals.

[0048] Example 15 This embodiment provides a method for preparing molecular perovskite energetic material spherulites. The molecular perovskite energetic material used is PAP-M4, the solvent is dimethyl sulfoxide, the preset temperature is 40℃, the crystal form regulator is PEG with a mass fraction of 10%, the antisolvent is ethyl acetate, and the volume ratio of the molecular perovskite energetic material / crystal form regulator saturated solution to the antisolvent is 1:10.

[0049] The steps are as follows: S0, Weigh 10 g of PAP-M4 into a beaker, add 20 mL of dimethyl sulfoxide, and in the temperature range of 20℃-70℃, take 5 mL of saturated supernatant and dry it in a drying oven at 40℃ for every 5℃ increase in temperature. Calculate the solubility of PAP-M4 in dimethyl sulfoxide at 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, and 70℃. S1. Based on the solubility of PAP-M4 in dimethyl sulfoxide at 40℃, calculate that the mass of PAP-M4 required to prepare a saturated solution of PAP-M4 is 10g and the volume of dimethyl sulfoxide is 20mL. S2, at 40℃, 10g of PAP-M4 and 5% of PEG were added to 20 mL of dimethyl sulfoxide and stirred until completely dissolved to prepare a saturated PAP-M4 / PEG solution. S3. At room temperature, 5 mL of saturated PAP-M4 / PEG solution was slowly added dropwise to 50 mL of ethyl acetate using a peristaltic pump at a rate of 12.5 mL / min, while the stirring rate was controlled at 500 r / min, to obtain a white suspension. S4. After stirring for another 30 minutes, the white suspension was filtered, washed, and dried to obtain PAP-M4 crystals.

[0050] Example 16 To determine the component size and morphology of the final products in the examples, scanning electron microscopy (SEM) was performed on the raw materials and the final products of Examples 1-8. SEM characterization: Hitachi, model: SU8100.

[0051] Scanning electron microscopy results as follows Figure 2 As shown.

[0052] from Figure 2 As shown in (b-c), the solvent type significantly affects the shape of DAP-4. In the recrystallized product of DAP-4 using dimethyl sulfoxide as the solvent, pyramidal crystals grow on the surface of the blocky crystals, gradually evolving into spherical crystals. However, in the recrystallized product using N,N-dimethylformamide as the solvent, most of the DAP-4 remains blocky, showing no tendency to grow into spherical crystals; only a very small number of blocky crystals exhibit a very small number of pyramidal crystals on their surface. Analysis indicates that dimethyl sulfoxide is more suitable than N,N-dimethylformamide as a solvent for preparing DAP-4 spheroids.

[0053] from Figure 2As shown in (b, d, e), the type of antisolvent has a significant impact on the shape of DAP-4. Recrystallization products using anhydrous ethanol as the antisolvent exhibit spherical crystals with pyramidal surfaces, showing a tendency to grow into spheres. In contrast, products using ethyl acetate and 1,2-dichloroethane as antisolvents both show tightly aggregated cubic shapes. This indicates that anhydrous ethanol is more suitable than ethyl acetate and 1,2-dichloroethane as the antisolvent for preparing DAP-4 spheroids.

[0054] from Figure 2 As can be seen from (b, f, g), as the antisolvent ratio increases, the pyramidal grains become more compact, and the sphericity of the crystals gradually increases. The optimal experimental conditions are a solvent-antisolvent ratio of 1:20.

[0055] from Figure 2 As can be seen from (b, h, i), the PVP content has a significant impact on the morphology of DAP-4 crystals. With the increase of PVP content, the sphericity of DAP-4 crystals gradually increases, and the optimal PVP mass fraction for preparing DAP-4 spheroids is 15%.

[0056] In summary, the experimental conditions of Example 8 are the optimal experimental conditions for preparing DAP-4 spherulites, namely, dimethyl sulfoxide (DMSO) as solvent, anhydrous ethanol as antisolvent, PVP as crystal form regulator, solvent to antisolvent volume ratio of 1:20, and crystal form regulator mass fraction of 15%.

[0057] Particle size and XRD tests were performed on the raw materials and in Example 8. Particle size tester: Dandong Better Instruments Co., Ltd., model: BT-9300ST.

[0058] Figure 3 In this text, S-DAP-4 represents the spherical DAP-4 prepared in Example 8, Raw DAP-4 represents the raw material DAP-4, and CCDC is the crystal number of DAP-4. Figure 3 It can be seen that the spherulites of the molecular perovskite energetic material described in Example 8 are the same substance as the raw material (DAP-4), and the XRD curve of Example 8 has fewer impurity peaks, indicating that the purity of the spherical product is higher than that of the raw material, and there are fewer impurities. Figure 5 It can be seen that the median particle size distribution of the final product in Example 8 is 3.12 μm, which is significantly smaller than that of the final product in Example 8. Figure 4 The median particle size distribution of the raw materials.

[0059] According to the impact sensitivity characteristic drop height method in GJB-770B-1997 and the BAM friction sensitivity test method, the sensitivity of the raw materials and the final product in Example 8 was tested.

[0060] Mechanical sensitivity testing methods: A WL-1 type impact sensitivity meter was used, and the characteristic drop height test was conducted according to the 601 impact sensitivity characteristic drop height method (2.5 kg drop weight; sample mass: 30 mg; sample number: 25) in GJB-770B-1997. Friction sensitivity was tested using an FSKM 10BAM friction sensitivity meter.

[0061] The results are shown in Table 1.

[0062] Table 1 Mechanical sensitivity of raw materials and the final product in Example 8 The test results show that the energetic material spherulites prepared by the method of molecular perovskite energetic material spherulites described in this invention have good insensitivity reduction advantages.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing spherulites of a molecular perovskite energetic material, characterized in that, Includes the following steps: S1, based on the solubility of the molecular perovskite energetic material in the solvent at a preset temperature, calculate the mass of the molecular perovskite energetic material and the volume of the solvent required to prepare a saturated solution of the molecular perovskite energetic material; S2, with the total mass of the molecular perovskite energetic material saturated solution and crystal form regulator being 100%, the mass of the crystal form regulator is calculated according to the mass fraction of the crystal form regulator being 5~15%. The molecular perovskite energetic material and crystal form regulator are added to the solvent at a preset temperature and completely dissolved to prepare a molecular perovskite energetic material / crystal form regulator saturated solution. S3, at a volume ratio of 1:10~20, the saturated solution of molecular perovskite energetic material / crystal form regulator prepared in step S2 is added dropwise to the antisolvent at room temperature and stirred to obtain a white suspension; S4. The white suspension obtained in step S3 is filtered, washed, and dried to obtain molecular perovskite energetic material spherulites.

2. The method for preparing molecular perovskite energetic material spherulites according to claim 1, characterized in that, Molecular perovskite energetic materials are perchlorate-based molecular perovskite energetic materials.

3. The method for preparing molecular perovskite energetic material spherulites according to claim 2, characterized in that, The energetic molecular perovskite materials are (H2dabco)[NH4(ClO4)3] (DAP-4), (H2dabco)[Na(ClO4)3] (DAP-1), (H2dabco)[K(ClO4)3] (DAP-2), (H2mpz)[NH4(ClO4)3] (PAP-M4), (H2pz)[NH4(ClO4)3] (PAP-4), (H2hpz)[NH4(ClO4)3] (PAP-H4), (H2dabco-O)[NH4(ClO4)3] (DAP-O4), (H2mdabco)[NH4(ClO4)3] (DAP-M4), (H2dabco)[NH3OH(ClO4)3] (DAP-6), and (H2dabco)[NH3OH(ClO4)3] (DAP-6). One of the [NH2NH3(ClO4)3] (DAP-7).

4. The method for preparing molecular perovskite energetic material spherulites according to claim 1, characterized in that, The preset temperature is 40℃-70℃.

5. The method for preparing molecular perovskite energetic material spherulites according to claim 1, characterized in that, The solvent is one of dimethyl sulfoxide and dimethylformamide.

6. The method for preparing molecular perovskite energetic material spherulites according to claim 1, characterized in that, The crystal form regulator is one of polyvinylpyrrolidone or polyethylene glycol.

7. The method for preparing molecular perovskite energetic material spherulites according to claim 1, characterized in that, The antisolvent is one of anhydrous ethanol, ethyl acetate, or 1,2-dichloroethane.

8. The method for preparing molecular perovskite energetic material spherulites according to claim 7, characterized in that, In step S3, the saturated solution of molecular perovskite energetic material / crystal form regulator is slowly added dropwise to the antisolvent at a rate of 12.5 mL / min using a peristaltic pump, while the stirring rate is controlled at 500 r / min.

9. A molecular perovskite energetic material spherulite, characterized in that, Prepared by the method for preparing molecular perovskite energetic material spherulites according to any one of claims 1-8.

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