Preparation method of graphene oxide induced assembled molecular perovskite energetic material
By inducing the assembly of molecular perovskite energetic materials using graphene oxide, the problem of high mechanical sensitivity in molecular perovskite energetic materials has been solved, thereby improving material safety and enabling mass production.
Patent Information
- Application Number
- CN202510885981.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-11-04
AI Technical Summary
Existing molecular perovskite energetic materials have high mechanical sensitivity, which affects their safety and practical applications.
Using graphene oxide as a carrier, DAP-4 crystal molecules are induced to assemble through functional groups on the surface of graphene oxide sheets, forming molecular perovskite energetic materials intercalated/embedded within the graphene oxide sheets, thereby improving the internal bonding strength of the crystal.
It reduces the mechanical sensitivity of the material, improves its safety, avoids the risk of breakage and hot spots under external force, and the preparation process is simple and efficient, allowing for mass production.
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Figure CN120887767A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of energetic materials, and relates to a molecular perovskite energetic material, in particular to a preparation method of a graphene oxide-induced assembly molecular perovskite energetic material. BACKGROUND
[0002] High-energy low-inductive energetic materials are one of the important methods to improve the safety of ammunition and solve the problem of battlefield survivability of future equipment. With the continuous in-depth research in the field of energetic materials, exploring and developing new types of energetic materials that meet the development needs has been regarded as the key to realizing the high-energy of explosive formulations. The molecular perovskite energetic material is a new type of organic-inorganic hybrid energetic compound discovered by Chen Xiaoming's research group of Sun Yat-sen University in 2018. The structure and composition of this type of energetic material are obviously different from traditional high-energy explosives, and the synthesis process is simple, the economic cost is low, and the thermal stability is good.
[0003] As a typical representative of molecular perovskite energetic materials, DAP-4 shows a level of detonation performance comparable to HMX (the measured explosion heat and detonation velocity are 5.691 kJ / g and 8.5 km / s, respectively); but the safety is comparable to CL-20, which has high impact sensitivity and friction sensitivity, which is not conducive to the practical application of molecular perovskite energetic materials. Therefore, improving the safety of DAP-4 material is an important link to promote its application.
[0004] A large number of researchers have carried out DAP-4 desensitization research by improving the morphology and particle size of DAP-4 and coating the surface of DAP-4 with a desensitizing substance (such as fluorine rubber, paraffin, polymer, insensitive explosive, etc.). The results show that although the above-mentioned methods improve the safety of the material to a certain extent, the impact sensitivity of the material is significantly reduced, but the friction sensitivity of DAP-4 is still high and has not been significantly improved, which still has a high risk in actual application, and further research on the crystal of the material is still needed. SUMMARY
[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide a preparation method of a graphene oxide-induced assembly molecular perovskite energetic material, which solves the technical problem that the mechanical sensitivity of the molecular perovskite energetic material in the prior art needs to be further reduced.
[0006] In order to solve the above technical problems, the technical scheme is adopted as follows:
[0007] A preparation method of a graphene oxide-induced assembly molecular perovskite energetic material, the method comprising the following steps:
[0008] Step one, configure the graphene oxide dispersion liquid, add ammonium perchlorate and perchloric acid into the graphene oxide dispersion liquid, stir until the solid particles are completely dissolved, and form an ammonium perchlorate-perchloric acid-graphene oxide precursor solution.
[0009] Step two, dissolve triethylenediamine in water to form a triethylenediamine solution, and add the triethylenediamine solution into the ammonium perchlorate-perchloric acid-graphene oxide precursor solution obtained in step one under stirring at a reaction temperature, and carry out the reaction at the reaction temperature.
[0010] Step three, after the reaction is completed, stir and cool, then separate the product, wash and dry, and collect the brown solid product, which is the graphene oxide induced assembled molecular perovskite energetic material.
[0011] The application also has the following technical features:
[0012] In step one, the graphene oxide dispersion liquid is a water dispersion solution of graphene oxide with a dispersion concentration in the range of 0.05 mg / mL to 5.0 mg / mL.
[0013] In step one, the addition amount of ammonium perchlorate in the ammonium perchlorate-perchloric acid-graphene oxide precursor solution is in the range of 0.05 to 0.7 g / mL, and the addition amount of perchloric acid in the precursor solution is in the range of 0.08 to 1.3 g / mL.
[0014] In step two, the concentration of the triethylenediamine solution is 0.15 to 2.1 g / mL.
[0015] In step two, the reaction temperature is 30 to 80℃.
[0016] In step two, the reaction time is 15 min to 120 min.
[0017] In step three, the stirring and cooling are to a temperature in the range of 5 to 10℃.
[0018] Preferably, in step one, the graphene oxide dispersion liquid is a water dispersion solution of graphene oxide with a dispersion concentration of 2.0 mg / mL, the addition amount of ammonium perchlorate in the ammonium perchlorate-perchloric acid-graphene oxide precursor solution is 0.5 g / mL, and the addition amount of perchloric acid in the precursor solution is 1.25 g / mL.
[0019] Preferably, in step two, the concentration of the triethylenediamine solution is 0.50 g / mL, the reaction temperature in step two is 50℃, and the reaction time is 120 min.
[0020] Preferably, in step three, the stirring and cooling are to a temperature of 5℃.
[0021] Compared with the prior art, the present application has the following technical effects:
[0022] (I) In the present application, graphene oxide is used as a carrier, and the DAP-4 crystal molecules are induced to assemble by the functional groups on the surface of the graphene oxide sheet, so that the graphene oxide sheet intercalation / inclusion type molecular perovskite energetic material is prepared. This method helps to improve the brittleness of the DAP-4 crystal and increase the internal bonding strength of the crystal, so that the crystal material is not easy to break and form a hot spot to cause explosion when subjected to external force, thereby helping to reduce the mechanical sensitivity of the material.
[0023] (II) Unlike the surface coating desensitization treatment in the prior art, the present application has the problems of incomplete surface coating and exposed crystals. In the method of the present application, the DAP-4 crystal is embedded in the graphene oxide sheet, and the material safety is improved from the inside of the crystal.
[0024] (III) The method of the present application uses graphene oxide dispersion liquid as the DAP-4 material synthesis mother liquor, and the preparation process is simple, efficient, reliable and can batch prepare the molecular perovskite energetic material.
[0025] (IV) The preparation process of the present application is simple, efficient, safe and reliable, which helps to batch prepare the DAP-4 energetic material with higher safety, thereby promoting its application in the field of explosive formulations. BRIEF DESCRIPTION OF DRAWINGS
[0026] Figure 1 It is a schematic diagram of the preparation mechanism of the molecular perovskite energetic material induced and assembled by graphene oxide.
[0027] Figure 2 It is an optical photograph of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by the induced assembly of the molecular perovskite energetic material and graphene oxide.
[0028] Figure 3 It is an SEM picture of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by the induced assembly of the molecular perovskite energetic material and graphene oxide.
[0029] Figure 4 It is an XRD picture of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by the induced assembly of the molecular perovskite energetic material and graphene oxide.
[0030] Figure 5 It is a DSC picture of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by the induced assembly of the molecular perovskite energetic material and graphene oxide.
[0031] Figure 6 It is a comparison chart of the friction sensitivity results of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by the induced assembly of the molecular perovskite energetic material and graphene oxide.
[0032] The specific content of the present application is further explained in detail in the following combined with examples. DETAILED DESCRIPTION
[0033] It should be noted that all materials and equipment in the present application, in the absence of special instructions, are known materials and equipment in the art. For example, DAP-4 and graphene oxide are commonly used DAP-4 and graphene oxide known in the art.
[0034] In the present application, the molecular perovskite energetic material is DAP-4, and the graphene oxide induced assembly molecular perovskite energetic material is GO@DAP-4. DAP-4 is a known compound with a molecular formula of (C6H 14 N2)[NH4(ClO4)3].
[0035] The following gives specific examples of the present application, it should be noted that the present application is not limited to the following specific examples, any equivalent transformation made on the basis of the technical scheme of the present application falls within the scope of the present application.
[0036] Example 1:
[0037] This embodiment gives a preparation method of graphene oxide induced assembly molecular perovskite energetic material, which comprises the following steps: configuring 0.05mg / mL of graphene oxide aqueous dispersion solution 30mL, adding appropriate amount of 3.0g ammonium perchlorate and 7.5g perchloric acid to the graphene oxide dispersion solution, stirring until dissolved uniformly and forming a brown yellow ammonium perchlorate-perchloric acid-graphene oxide precursor solution. 2.8g of triethylenediamine is dissolved in 20mL of deionized water to form a colorless transparent triethylenediamine solution. At 30℃, slowly add the triethylenediamine solution to the ammonium perchlorate-perchloric acid-graphene oxide precursor solution under stirring, and after 15min of reaction at this temperature, reduce the temperature to 10℃ under stirring. Finally, after separation, washing and drying, the brown solid product is collected, which is the graphene oxide induced assembly molecular perovskite energetic material.
[0038] Example 2:
[0039] The embodiment provides a preparation method of a graphene oxide induced assembly molecular perovskite energetic material, which comprises the following steps: 40 mL of 0.5 mg / mL graphene oxide aqueous dispersion solution is configured, and appropriate amounts of 2.0 g ammonium perchlorate and 5.0 g perchloric acid are added into the graphene oxide dispersion solution, and stirring is performed until the solution is uniformly dissolved and a brown-yellow ammonium perchlorate-perchloric acid-graphene oxide precursor solution is formed. 1.9 g of triethylenediamine is dissolved in 10 mL of deionized water to form a colorless and transparent triethylenediamine solution. The triethylenediamine solution is slowly added into the ammonium perchlorate-perchloric acid-graphene oxide precursor solution under stirring at 50 DEG C, and after reaction at the temperature for 60 min, the temperature is reduced to 5 DEG C under stirring. Finally, a brown solid product, namely the graphene oxide induced assembly molecular perovskite energetic material, is collected after separation, washing and drying.
[0040] Embodiment 3
[0041] The embodiment provides a preparation method of a graphene oxide induced assembly molecular perovskite energetic material, which comprises the following steps: 40 mL of 0.5 mg / mL graphene oxide aqueous dispersion solution is configured, and appropriate amounts of 2.0 g ammonium perchlorate and 5.0 g perchloric acid are added into the graphene oxide dispersion solution, and stirring is performed until the solution is uniformly dissolved and a brown-yellow ammonium perchlorate-perchloric acid-graphene oxide precursor solution is formed. 1.9 g of triethylenediamine is dissolved in 10 mL of deionized water to form a colorless and transparent triethylenediamine solution. The triethylenediamine solution is slowly added into the ammonium perchlorate-perchloric acid-graphene oxide precursor solution under stirring at 50 DEG C, and after reaction at the temperature for 60 min, the temperature is reduced to 5 DEG C under stirring. Finally, a brown solid product, namely the graphene oxide induced assembly molecular perovskite energetic material, is collected after separation, washing and drying.
[0042] Embodiment 4
[0043] The embodiment provides a preparation method of a graphene oxide induced assembly molecular perovskite energetic material, which comprises the following steps: 40 mL of 0.5 mg / mL graphene oxide aqueous dispersion solution is configured, and appropriate amounts of 2.0 g ammonium perchlorate and 5.0 g perchloric acid are added into the graphene oxide dispersion solution, and stirring is performed until the solution is uniformly dissolved and a brown-yellow ammonium perchlorate-perchloric acid-graphene oxide precursor solution is formed. 1.9 g of triethylenediamine is dissolved in 10 mL of deionized water to form a colorless and transparent triethylenediamine solution. The triethylenediamine solution is slowly added into the ammonium perchlorate-perchloric acid-graphene oxide precursor solution under stirring at 50 DEG C, and after reaction at the temperature for 60 min, the temperature is reduced to 5 DEG C under stirring. Finally, a brown solid product, namely the graphene oxide induced assembly molecular perovskite energetic material, is collected after separation, washing and drying.
[0044] In the embodiment, Figure 1The preparation mechanism diagram of graphene oxide inducing assembly of molecular perovskite energetic material is shown, Figure 2 The optical photos of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by graphene oxide inducing assembly are compared. It is obvious that the DAP-4 material is pure white, and the graphene oxide inducing assembly DAP-4 is brownish yellow. Figure 3 The SEM images of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by graphene oxide inducing assembly are compared. It can be found that the micro surface of the DAP-4 material is relatively smooth, and the surface of the graphene oxide inducing assembly DAP-4 appears more defects. This is because the adsorption and assembly of the surface functional groups of the graphene oxide to the ions induce the change of the DAP-4 crystallization process, and the DAP-4 crystals are intercalated by the graphene oxide. Figure 4 The XRD curves of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by graphene oxide inducing assembly are compared. It can be seen that the presence of graphene oxide only changes the crystallization process of DAP-4, does not cause the change of DAP-4 material, and does not introduce other impurities in the system. Figure 5 The DSC curves of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by graphene oxide inducing assembly are compared. After the DAP-4 is induced and assembled by the graphene oxide, the exothermic peak is relatively advanced and concentrated, indicating that the presence of graphene oxide catalyzes the thermal decomposition performance of DAP-4. Figure 6 The friction sensitivity results of the molecular perovskite energetic material and the molecular perovskite energetic material prepared by graphene oxide inducing assembly are further compared. It can be seen that the friction sensitivity of the molecular perovskite energetic material prepared by graphene oxide inducing assembly is 42N measured by BAM (Federal Institute for Materials Testing) test method (i.e. BAM Test Method), and the friction sensitivity of the original molecular perovskite energetic material is 28N, indicating that the graphene oxide induction obviously changes the friction sensitivity of the DAP-4 material.
[0045] Example 5:
[0046] The embodiment provides a preparation method of graphene oxide induced assembly molecular perovskite energetic material, and the method comprises the following steps: configuring 100 mL of 1.0 mg / mL graphene oxide water dispersion solution, adding appropriate amounts of 30 g ammonium perchlorate and 75 g perchloric acid into the graphene oxide dispersion solution, stirring until the ammonium perchlorate-perchloric acid-graphene oxide precursor solution is uniformly dissolved and brown yellow is formed. 28 g of triethylenediamine is dissolved in 60 mL of deionized water to form a colorless transparent triethylenediamine solution. At 40 DEG C, the triethylenediamine solution is slowly added to the ammonium perchlorate-perchloric acid-graphene oxide precursor solution under stirring, and after 45 min of reaction at the temperature, the stirring is cooled to 10 DEG C. Finally, the brown solid product, i.e., the graphene oxide induced assembly molecular perovskite energetic material, is collected after separation, washing and drying.
Claims
1. A method for preparing a graphene oxide-induced assembled molecular perovskite energetic material, characterized in that, The method includes the following steps: Step 1: Prepare graphene oxide dispersion by adding ammonium perchlorate and perchloric acid to the graphene oxide dispersion and stirring until the solid particles are completely dissolved to form an ammonium perchlorate-perchloric acid-graphene oxide precursor solution. Step 2: At the reaction temperature, triethylenediamine is dissolved in water to form a triethylenediamine solution. Under stirring, the triethylenediamine solution is added to the ammonium perchlorate-perchloric acid-graphene oxide precursor solution obtained in Step 1, and the reaction is carried out at the reaction temperature. Step 3: After the reaction is complete, stir and cool down, then separate the products, wash and dry them to collect the brown solid product, which is the graphene oxide-induced assembled molecular perovskite energetic material.
2. The method for preparing graphene oxide-induced assembled molecular perovskite energetic materials as described in claim 1, characterized in that, In step one, the graphene oxide dispersion is an aqueous dispersion of graphene oxide with a dispersion concentration in the range of 0.05 mg / mL to 5.0 mg / mL.
3. The method for preparing graphene oxide-induced assembled molecular perovskite energetic materials as described in claim 1, characterized in that, In step one, the amount of ammonium perchlorate added to the ammonium perchlorate-perchloric acid-graphene oxide precursor solution is in the range of 0.05 to 0.7 g / mL, and the amount of perchloric acid added to the precursor solution is in the range of 0.08 to 1.3 g / mL.
4. The method for preparing graphene oxide-induced assembled molecular perovskite energetic materials as described in claim 1, characterized in that, In step two, the concentration of the triethylenediamine solution is 0.15–2.1 g / mL.
5. The method for preparing graphene oxide-induced assembled molecular perovskite energetic materials as described in claim 1, characterized in that, In step two, the reaction temperature is 30℃~80℃.
6. The method for preparing the graphene oxide-induced assembled molecular perovskite energetic material as described in claim 1, characterized in that, In step two, the reaction time is 15 min to 120 min.
7. The method for preparing the graphene oxide-induced assembled molecular perovskite energetic material as described in claim 1, characterized in that, In step three, the mixture is stirred and cooled to a temperature range of 5–10°C.
8. The method for preparing graphene oxide-induced assembled molecular perovskite energetic materials as described in claim 1, characterized in that, In step one, the graphene oxide dispersion is an aqueous dispersion solution of graphene oxide with a dispersion concentration of 2.0 mg / mL; the amount of ammonium perchlorate added in the ammonium perchlorate-perchloric acid-graphene oxide precursor solution is 0.5 g / mL, and the amount of perchloric acid added in the precursor solution is 1.25 g / mL. In step two, the concentration of the triethylenediamine solution is 0.50 g / mL; in step two, the reaction temperature is 50°C; and the reaction time is 120 min. In step three, stir and cool down to 5°C.