ADN-based metal ion nitrogen-containing complex energetic material as well as preparation method and application thereof

Abstract

The invention discloses an ADN-based metal ion nitrogen-containing complex energetic material as well as a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing a solution containing a nitrogen-containing ligand and a mixed solution containing soluble metal salt and ammonium dinitramide, and standing to obtain the ADN-based metal ion nitrogen-containing complex energetic material. The ADN-based metal nitrogen-containing complex energetic material prepared by the invention has relatively high energy and moisture absorption resistance, and the preparation method is simple, low in cost and suitable for large-scale production.

Description

Technical Field

[0001] The present invention specifically relates to an ADN-based metal ion nitrogen-containing complex energetic material, a preparation method thereof, and an application thereof. Background Art

[0002] For a flying cruiser, power comes first. As the energy source and working medium source of a solid rocket motor, a solid propellant is composed of a fuel, an oxidizer, and functional additives. Its energy performance and safety performance are related to the combat effectiveness and survivability of strategic and tactical missiles. Developing high-energy oxidizers is an effective way to develop new solid propellants with high specific impulse and large thrust. Ammonium dinitramide (ADN, NH 4 N(NO 2 ) 2 ), is a new type of halogen- and carbon-free high-energy green oxidizer. Its oxygen balance is 25.8% (calculated based on CO 2 ), the crystal density is 1.812 g / cm 3 , and the heat of formation is -148.4 kJ / mol. It can be used as both an explosive and an oxidizer component of a solid propellant. Compared with ammonium perchlorate (AP), which is commonly used as an oxidizer in current solid propellants, it has the characteristics of chlorine-free, low characteristic signal, and high heat of formation. It is one of the new generation of high-energy components of solid propellants with development prospects urgently needed for future strategic and tactical missiles. However, the ammonium cation (NH 4 + ) and the dinitramide anion (N(NO 2 ) 2 - ) in the ADN molecule are extremely easy to form hydrogen bonds with water and have extremely strong hygroscopicity, which seriously affects the preparation, storage, safety performance, and energy performance of ADN-based solid propellants. It is also a technical bottleneck that severely restricts the large-scale engineering application of ADN at present and urgently needs to be solved. Therefore, solving the hygroscopicity of ADN is a bottleneck technology for its large-scale application in the fields of composite explosives and solid propellants.

[0003] At present, there are mainly three methods at home and abroad for reducing the hygroscopicity of ADN: one is the spheroidization granulation and crystal morphology control technology, which controls the morphology of ADN to make the particle morphology tend to be spherical and reduce the hygroscopicity; the second is the coating technology, which uses a moisture-proof material to coat the surface of ADN to isolate the contact between ADN molecules and water molecules; the third is the eutectic technology, which makes ADN form a eutectic with other energetic materials to improve its physical and chemical properties. At present, the modification of ADN not only has a complex preparation method but also the hygroscopicity has not been significantly improved. For example, the Swedish FOI company uses the ADN emulsion spheroidization technology to obtain spherical ADN with a particle size of about 700 μm; Li Lei et al. from Hubei Institute of Aerospace Chemical Technology screened a certain type of coating material according to the calculated interfacial energy. At 30 °C and a relative humidity of 75%, its saturated moisture absorption rate decreased from 55% to less than 2.5%; Wang Haojing et al. from North University of China prepared an ADN / 18C6 eutectic with a molar ratio of 1:1 by the solvent evaporation method. Through the moisture absorption rate measurement experiment, it was found that at 30 °C, 80% relative humidity, and a time of 12 h, the hygroscopicities of ADN and ADN / 18C6 eutectic were 18% and 1.2% respectively, indicating that the ADN / 18C6 eutectic can significantly reduce the hygroscopicity, but spheroidization granulation did not change the characteristic that ADN easily forms hydrogen bonds with water molecules; surface coating is limited by factors such as the optimal coating agent, the best coating process, and the compactness of the coating layer, and can only delay the moisture absorption process of ADN; while eutectic modification is limited by energy factors and has not been realized in industrial applications yet. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the defects of easy hygroscopicity and complex modification methods in the prior art, and provide an ADN-based metal ion nitrogen-containing complex energetic material, its preparation method, and application. The ADN-based metal nitrogen-containing complex energetic material prepared by the present invention has high energy and moisture resistance, and the preparation method is simple, the cost is low, and it is suitable for large-scale production.

[0005] The present invention prepares an ADN-based metal ion nitrogen-containing complex energetic material by uniformly mixing a solution containing a nitrogen-containing ligand and a "mixed solution containing a soluble metal salt and ammonium dinitramide" and then standing. The preparation method is not only simple, but also the prepared ADN-based metal ion nitrogen-containing complex energetic material has high energy and moisture resistance. The present invention starts from the cations and anions on the surface of ADN. First, metal ions are used to replace NH on the surface of ADN 4 + , and then a nitrogen-containing ligand is introduced, so that the metal ions coordinate with the N atoms in the nitrogen-containing ligand molecule and the O atoms in the anion N(NO 2 ) 2 - to prepare the compound ADN-based metal ion nitrogen-containing complex energetic material.

[0006] The present invention solves the above technical problems through the following technical solutions:

[0007] The present invention provides a preparation method of an ADN-based metal ion nitrogen-containing complex energetic material, which comprises the following steps:

[0008] A solution containing a nitrogen-containing ligand and a "mixed solution containing a soluble metal salt and ammonium dinitramide" are mixed evenly and then allowed to stand to obtain the ADN-based metal ion nitrogen-containing complex energetic material.

[0009] In the present invention, preferably, the solution containing the nitrogen-containing ligand is added to the mixed solution containing the soluble metal salt and ammonium dinitramide. More preferably, the solution containing the nitrogen-containing ligand is added to the mixed solution containing the soluble metal salt and ammonium dinitramide through a dropping device. The dropping device can be conventional in the art, generally a peristaltic pump device, a dropper, a dropping funnel or a syringe, preferably a peristaltic pump device; it is easier to control the dropping rate and ensure the stability of the sample batch by using a peristaltic pump device for dropping. During the adding process, the dropping rate is preferably 0.2 - 4 mL / min, more preferably 0.5 - 2 mL / min, such as 0.5 mL / min, 1.0 mL / min or 1.5 mL / min. According to the convention in the art, generally, the solution containing the nitrogen-containing ligand is added to the mixed solution containing the soluble metal salt and ammonium dinitramide under stirring.

[0010] In the present invention, the mixing time can be 10 - 120 min, preferably 30 - 60 min, such as 30 min, 45 min, 60 min or 90 min. The mixing is generally carried out at room temperature. The room temperature is generally 15 - 35 °C, such as 20 °C or 25 °C. The mixing method can be conventional in the art, such as stirring or ultrasonic. The stirring rate can be 200 - 1000 r / min, preferably 400 - 800 r / min, such as 500 r / min or 600 r / min.

[0011] In some preferred embodiments, the preparation method of the ADN-based metal ion nitrogen-containing complex energetic material comprises the following steps: adding a solution containing a nitrogen-containing ligand to a mixed solution containing a soluble metal salt and ammonium dinitramide, mixing evenly and then allowing to stand to obtain the ADN-based metal ion nitrogen-containing complex energetic material.

[0012] In some more preferred embodiments, the preparation method of the ADN-based metal ion nitrogen-containing complex energetic material comprises the following steps: at room temperature, adding a solution containing a nitrogen-containing ligand to a mixed solution containing a soluble metal salt and ammonium dinitramide, mixing evenly and then allowing to stand to obtain the ADN-based metal ion nitrogen-containing complex energetic material.

[0013] In the present invention, the standing time can be 10 - 120 min, preferably 20 - 40 min, such as 30 min. The standing is generally carried out at room temperature. Particle precipitation will occur during the standing process. According to the routine in the art, solid-liquid separation, washing, and drying are generally required after the standing. The method of solid-liquid separation can be conventional in the art, such as filtration.

[0014] In the present invention, the nitrogen-containing ligand generally refers to an organic or inorganic molecule containing a coordinatable nitrogen atom. Usually, the nitrogen atom in the ligand can provide a lone pair of electrons and can be used as a ligand to coordinate with metal ions. Preferably, it is one or more of ammonia, imidazole, 4-amino-1,2,4-triazol-5-one, 4,4'-azo-1,2,4-triazole, and 5-amino-1H-tetrazole, and more preferably, it is one or more of ammonia, imidazole, and 5-amino-1H-tetrazole.

[0015] In the present invention, the solvent in the solution containing the nitrogen-containing ligand can be deionized water and / or ethanol.

[0016] In the present invention, the concentration of the solution containing the nitrogen-containing ligand can be 0.01 - 2.0 mol / mL, such as 0.03 mol / mL, 0.4 mol / mL, 0.5 mol / mL, 0.8 mol / mL, 1.0 mol / mL, 1.3 mol / mL, or 1.6 mol / mL.

[0017] In certain embodiments, when the solution containing the nitrogen-containing ligand is ammonia water, the mass fraction of ammonia water can be 25% - 28%.

[0018] In the present invention, when the nitrogen-containing ligand itself exists in a state dissolved in a solvent (such as ammonia water), it can be directly used; when the nitrogen-containing ligand is a solid powder, generally, the nitrogen-containing ligand is added to a solvent to prepare a solution for use.

[0019] In the present invention, according to the solubility of the nitrogen-containing ligand, it can be dissolved in a solvent at room temperature or under heating conditions. The preparation method of the solution containing the nitrogen-containing ligand preferably includes the following steps: dissolving the nitrogen-containing ligand in a solvent and mixing evenly.

[0020] Among them, the method of mixing can be conventional in the art, such as magnetic stirring, mechanical stirring, or ultrasonic treatment. The mixing time can be 5 - 50 min, preferably 5 - 30 min, such as 10 min, 15 min, 20 min, or 30 min; the mixing temperature is preferably 15 - 60 °C, such as 25 °C, 30 °C, 40 °C, or 50 °C.

[0021] In the present invention, the soluble metal salt generally refers to a metal salt that is easily soluble in water, preferably a soluble transition metal salt, more preferably one or more of copper nitrate trihydrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate, and zinc nitrate hexahydrate.

[0022] In the present invention, the solvent in the mixed solution containing the soluble metal salt and ammonium dinitramide can be one or more of deionized water, ethanol, acetone, and ethyl acetate.

[0023] In the present invention, in the mixed solution containing the soluble metal salt and ammonium dinitramide, the concentration of the soluble metal salt can be 0.05 - 2.0 mol / mL, preferably 0.1 - 1.0 mol / mL, such as 0.2 mol / mL, 0.3 mol / mL, 0.5 mol / mL, or 0.8 mol / mL.

[0024] In some preferred embodiments, the soluble metal salt is copper nitrate trihydrate, and the nitrogen-containing ligand is one or more of ammonia, imidazole, and 5-amino-1H-tetrazole.

[0025] In a more preferred embodiment, the soluble metal salt is copper nitrate trihydrate, and the nitrogen-containing ligand is imidazole.

[0026] In some preferred embodiments, the soluble metal salt is cobalt nitrate hexahydrate, and the nitrogen-containing ligand is one or more of ammonia, imidazole, and 5-amino-1H-tetrazole.

[0027] In a more preferred embodiment, the soluble metal salt is cobalt nitrate trihydrate, and the nitrogen-containing ligand is 5-amino-1H-tetrazole.

[0028] In the present invention, the morphology of ammonium dinitramide can be conventional in the art, generally needle-shaped, flake-shaped, or spherical.

[0029] In the present invention, the molar ratio of the metal ion in the soluble metal salt to the ammonium dinitramide is generally determined according to the coordination number of the metal ion. When the metal ion in the soluble metal salt is a divalent metal ion, the molar ratio of the metal ion in the soluble metal salt to the ammonium dinitramide is preferably 1:(2 - 6), such as 1:2, 1:4, or 1:6. When the metal ion in the soluble metal salt is a trivalent metal ion, the molar ratio of the metal ion in the soluble metal salt to the ammonium dinitramide is preferably 1:(3 - 9), such as 1:3.

[0030] In the present invention, the molar ratio of the soluble metal salt to the nitrogen-containing ligand is generally determined according to the coordination number of the metal ion and the number of N atoms capable of coordination in the nitrogen-containing ligand. When the metal ion in the soluble metal salt is a divalent metal ion and the number of N atoms capable of coordination in the nitrogen-containing ligand is 1, the molar ratio of the metal ion in the soluble metal salt to the nitrogen-containing ligand is preferably 1:(4 - 12), such as 1:4 or 1:8. When the metal ion in the soluble metal salt is a divalent metal ion and the number of N atoms capable of coordination in the nitrogen-containing ligand is 2, the molar ratio of the metal ion in the soluble metal salt to the nitrogen-containing ligand is preferably 1:(2 - 6), such as 1:2 or 1:4.

[0031] In the present invention, the preparation method of the mixed solution containing the soluble metal salt and ammonium dinitramide preferably includes the following steps: adding a mixture of the soluble metal salt and ammonium dinitramide into a solvent, and mixing uniformly at room temperature.

[0032] Among them, the mixing method can be conventional in the art, such as magnetic stirring, mechanical stirring or ultrasonic treatment. The mixing time can be 5 - 60 min, preferably 5 - 30 min, such as 10 min, 15 min, 20 min or 30 min. The room temperature is generally 15 - 35 °C, such as 20 °C or 25 °C.

[0033] The present invention also provides an ADN-based metal nitrogen-containing complex energetic material prepared by the preparation method as described above.

[0034] The present invention also provides an application of the ADN-based metal nitrogen-containing complex energetic material as described above as a high-energy oxidizer or a low-sensitivity burning rate catalyst in high-energy solid propellants.

[0035] On the basis of conforming to common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred examples of the present invention.

[0036] The reagents and raw materials used in the present invention are all commercially available.

[0037] The positive and progressive effects of the present invention are as follows:

[0038] (1) The preparation method of the present invention is simple, the reaction conditions are mild, the crystallization is rapid, and the product is easy to separate, which has important engineering value and reference significance for the anti-moisture modification of ADN; and the cost is low and it is suitable for large-scale production;

[0039] (2) The ADN-based metal nitrogen-containing complex energetic material prepared by the present invention has high energy and anti-moisture performance. Description of the Drawings

[0040] Figure 1SEM images and optical photos of the ADN-based metal ion nitrogen-containing complex energetic materials prepared in Examples 1-3;

[0041] Figure 2 Moisture absorption rate change curves of the ADN-based metal ion nitrogen-containing complex energetic materials and ADN raw materials prepared in Examples 1-3;

[0042] Figure 3 SEM images and optical photos of the ADN-based metal ion nitrogen-containing complex energetic materials prepared in Examples 4-6;

[0043] Figure 4 Moisture absorption rate change curves of the ADN-based metal ion nitrogen-containing complex energetic materials and ADN raw materials prepared in Examples 4-6. Detailed implementation manners

[0044] The present invention will be further illustrated by the following examples, but the present invention is not limited to the scope of the described examples. For the experimental methods without specific conditions noted in the following examples, they are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0045] Example 1

[0046] Step 1: At room temperature, dissolve 1 mol of copper nitrate trihydrate and 2 mol of ammonium dinitramide (lamellar structure) in 5 mL of deionized water, and stir for 15 min to obtain a dinitramide ammonium solution containing metal ions;

[0047] Step 2: At room temperature, dissolve 4 mol of imidazole (IMI) in 3 mL of deionized water, and stir for 10 min to obtain a nitrogen-containing ligand solution;

[0048] Step 3: At room temperature, under stirring, add the nitrogen-containing ligand solution dropwise to the above-mentioned dinitramide ammonium solution containing metal ions through a peristaltic pump device (Lever Fluid, BT100S) at a rate of 1 mL / min, and then continue to stir at a stirring rate of 500 rpm for 60 min to obtain a uniformly mixed solution;

[0049] Step 4: At room temperature, let the above-mentioned mixed solution stand for 30 min until granular precipitation occurs. Filter, wash, and dry the precipitate to obtain the ADN-based metal ion nitrogen-containing complex energetic material Cu(IMI)DN. Calculated based on the ADN feed amount, the yield is 82.4% (precipitate mass / ADN feed amount).

[0050] Example 2

[0051] Step 1: At room temperature, dissolve 1 mol of copper nitrate trihydrate and 2 mol of ammonium dinitramide in 5 mL of deionized water, and stir for 15 min to obtain a dinitramide ammonium solution containing metal ions;

[0052] Step 2: Dissolve 4 mol of 5-amino-1H-tetrazole (ATZ) in 5 mL of ethanol, heat at 40 °C, and stir for 10 min to obtain a nitrogen-containing ligand solution;

[0053] Step 3: At room temperature, while stirring, add the nitrogen-containing ligand solution dropwise to the above-mentioned ammonium dinitramide solution containing metal ions through a peristaltic pump device at a rate of 1 mL / min, and then continue to stir at a stirring rate of 500 rpm for 60 min to obtain a uniformly mixed solution;

[0054] Step 4: At room temperature, let the above-mentioned mixed solution stand for 30 min until granular precipitation occurs. Filter, wash, and dry the precipitate to obtain an energetic material Cu(ATZ)DN of an ADN-based metal ion nitrogen-containing complex. Calculated based on the ADN feed amount, the yield is 71.3% (precipitate mass / ADN feed amount).

[0055] Example 3

[0056] Step 1: At room temperature, dissolve 1 mol of copper nitrate trihydrate and 2 mol of ammonium dinitramide in 5 mL of deionized water, and stir for 15 min to obtain an ammonium dinitramide solution containing metal ions;

[0057] Step 2: At room temperature, add 4 mol of ammonia water (NH 3 ·H 2 O, mass fraction 25%-28%) dropwise to the above-mentioned ammonium dinitramide solution containing metal ions through a peristaltic pump device at a rate of 1 mL / min, and then continue to stir at a stirring rate of 500 rpm for 60 min to obtain a uniformly mixed solution;

[0058] Step 3: At room temperature, let the above-mentioned mixed solution stand for 30 min while stirring until granular precipitation occurs. Filter, wash, and dry the precipitate to obtain an energetic material Cu(NH 3 )DN of an ADN-based metal ion nitrogen-containing complex. Calculated based on the ADN feed amount, the yield is 75.6% (precipitate mass / ADN feed amount).

[0059] Example 4

[0060] Step 1: Except for adjusting the soluble metal salt to cobalt nitrate hexahydrate, the other operations and conditions are the same as in Example 1;

[0061] Step 2: The same as in Example 1;

[0062] Step 3: The same as in Example 1;

[0063] Step 4: The same as Example 1; the energetic material Co(IMI)DN of the ADN-based metal ion nitrogen-containing complex was obtained, and the yield was 84.6% (precipitate mass / ADN feed amount) calculated based on the ADN feed amount.

[0064] Example 5

[0065] Step 1: Except that the soluble metal salt was adjusted to cobalt nitrate hexahydrate, the remaining operations and conditions were the same as those in Example 2;

[0066] Step 2: The same as Example 2;

[0067] Step 3: The same as Example 2;

[0068] Step 4: The same as Example 2; the energetic material Co(ATZ)DN of the ADN-based metal ion nitrogen-containing complex was obtained, and the yield was 86.5% (precipitate mass / ADN feed amount) calculated based on the ADN feed amount.

[0069] Example 6

[0070] Step 1: Except that the soluble metal salt was adjusted to cobalt nitrate hexahydrate, the remaining operations and conditions were the same as those in Example 3;

[0071] Step 2: The same as Example 3;

[0072] Step 3: The same as Example 3;

[0073] Step 4: The same as Example 3; the energetic material Co(NH 3 )DN of the ADN-based metal ion nitrogen-containing complex was obtained, and the yield was 79.5% (precipitate mass / ADN feed amount) calculated based on the ADN feed amount.

[0074] Comparative Example 1

[0075] ADN raw material.

[0076] Comparative Example 2

[0077] Except that copper nitrate trihydrate was not added in Step 1, the remaining experimental procedures were the same as those in Example 1, and no complex precipitate particles were obtained after the obtained mixed solution was allowed to stand.

[0078] Effect Example

[0079] (1) Morphology and Structure Characterization

[0080] Figure 1 SEM images and optical photos of the energetic materials of the ADN-based metal ion nitrogen-containing complexes prepared in Examples 1-3 are shown. According to Figure 1It can be seen that the Cu(IMI)DN prepared in Example 1 has a relatively high crystallinity and presents a regular dark blue crystal structure; the Cu(ATZ)DN prepared in Example 2 has a relatively poor crystallinity, shows an irregular morphology, and has an emerald green luster; the Cu(NH 3 )DN consists of clusters composed of many thin layer structures, has a small crystal size, and its color is dark purple.

[0081] Figure 3 SEM images and optical photos of the ADN-based metal ion nitrogen-containing complex energetic materials prepared in Examples 4-6. According to Figure 3 It can be seen that the Co(IMI)DN prepared in Example 4 has a relatively poor crystallinity and shows a light pink irregular morphology; the Co(ATZ)DN prepared in Example 5 has a relatively high crystallinity and presents a transparent lamellar structure; the Co(NH 3 )DN prepared in Example 6 has a relatively high crystallinity and presents a dark green spherical cluster structure.

[0082] (2) Hygroscopicity rate test

[0083] According to the desiccator equilibrium method in the national military standard (GJB 770A-97), the moisture absorption weight gain tests were respectively carried out on the ADN-based metal ion nitrogen-containing complex energetic materials prepared in Examples 1-6 and the ADN raw material in Comparative Example 1 in equal amounts. The principle of this method is: place a quantitative sample at a constant temperature and humidity (20 °C and 75% RH), measure the weight at regular intervals, and when the sample reaches the equilibrium state of moisture absorption, measure the mass of water absorbed by the sample, so as to calculate the final moisture absorption weight gain of the sample; the hygroscopicity rate = (weight after moisture absorption - weight before moisture absorption) / weight before moisture absorption × 100%.

[0084] Figure 2 The hygroscopicity rate change curves of the ADN-based metal ion nitrogen-containing complex energetic materials prepared in Examples 1-3 and the ADN raw material in Comparative Example 1. According to Figure 2 It can be seen that after 5 days of moisture absorption, the moisture absorption weight gain rate of the ADN raw material is 39.4%, the hygroscopicity rate of the Cu(IMI)DN prepared in Example 1 is 0.3%, and the hygroscopicity rate is reduced by 99.2%; the hygroscopicity rate of the Cu(ATZ)DN prepared in Example 2 is 4.7%, and the hygroscopicity rate is reduced by 88.1%; the hygroscopicity rate of the Cu(NH 3 )DN prepared in Example 3 is 1.8%, and the hygroscopicity rate is reduced by 95.4%.

[0085] Figure 4 The hygroscopicity rate change curves of the ADN-based metal ion nitrogen-containing complex energetic materials prepared in Examples 4-6 and the ADN raw material in Comparative Example 1. According to Figure 4It can be seen that the moisture absorption rate of Co(IMI)DN prepared in Example 4 is 1.5%, and the moisture absorption rate is reduced by 96.2%; the moisture absorption rate of Co(ATZ)DN prepared in Example 5 is 0.2%, and the moisture absorption rate is reduced by 99.5%; the moisture absorption rate of Co(NH 3 )DN prepared in Example 6 is 6.2%, and the moisture absorption rate is reduced by 84.3%.

[0086] Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that this is only an example. The protection scope of the present invention is defined by the appended claims. Without departing from the principle and essence of the present invention, those skilled in the art can make various changes or modifications to these embodiments, but these changes and modifications all fall within the protection scope of the present invention.

Claims

1. A method for preparing an ADN-based metal ion nitrogen-containing complex energetic material, characterized in that: It includes the following steps: The solution containing the nitrogen-containing ligand and the "mixed solution containing the soluble metal salt and ammonium dinitramide" are mixed evenly and then allowed to stand to obtain the ADN-based metal ion nitrogen-containing complex energetic material.

2. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: Adding a solution containing a nitrogen-containing ligand to a mixed solution containing a soluble metal salt and ammonium dinitramide, preferably, adding the solution containing a nitrogen-containing ligand to the mixed solution containing a soluble metal salt and ammonium dinitramide through a dropping device; The dropping device is preferably a peristaltic pump device, a rubber-tipped dropper, a dropping funnel or a syringe; during the adding process, the dropping rate is preferably 0.2-4 mL / min, more preferably 0.5-2 mL / min, such as 0.5 mL / min, 1.0 mL / min or 1.5 mL / min.

3. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: The mixing time is 10-120 min, preferably 30-60 min, for example 30 min, 45 min, 60 min or 90 min; and / or, the mixing is performed at room temperature; And / or, the standing time may be 10-120 min, preferably 20-40 min, for example 30 min.

4. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: The nitrogen-containing ligand satisfies one or more of the following conditions: (1) The nitrogen-containing ligand is one or more of ammonia, imidazole, 4-amino-1,2,4-triazol-5-one, 4,4′-azo-1,2,4-triazole and 5-amino-1H-tetrazole, preferably one or more of ammonia, imidazole and 5-amino-1H-tetrazole; (2) The solvent in the solution containing the nitrogen-containing ligand is deionized water and / or ethanol; (3) The concentration of the solution containing the nitrogen-containing ligand is 0.01-2.0 mol / mL, for example, 0.03 mol / mL, 0.4 mol / mL, 0.5 mol / mL, 0.8 mol / mL, 1.0 mol / mL, 1.3 mol / mL or 1.6 mol / mL; (4) The method for preparing the solution containing nitrogen-containing ligands comprises the following steps: dissolving the nitrogen-containing ligands in a solvent and mixing them evenly; wherein the mixing time is preferably 5-50 min, more preferably 5-30 min, for example, 10 min, 15 min, 20 min or 30 min; the mixing temperature is preferably 15-60°C, for example, 25°C, 30°C, 40°C or 50°C.

5. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: When the solution containing nitrogen-containing ligands is ammonia water, the mass fraction of ammonia water is 25%-28%.

6. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: The mixed solution containing the soluble metal salt and ammonium dinitramide satisfies one or more of the following conditions: (1) The soluble metal salt is a soluble transition metal salt, preferably one or more of copper nitrate trihydrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate and zinc nitrate hexahydrate; (2) The solvent in the mixed solution containing the soluble metal salt and ammonium dinitramide is one or more of deionized water, ethanol, acetone and ethyl acetate; (3) In the mixed solution containing the soluble metal salt and ammonium dinitramide, the concentration of the soluble metal salt is 0.05-2.0 mol / mL, preferably 0.1-1.0 mol / mL, such as 0.2 mol / mL, 0.3 mol / mL, 0.5 mol / mL or 0.8 mol / mL; (4) The method for preparing the mixed solution containing a soluble metal salt and ammonium dinitramide comprises the following steps: adding the mixture of the soluble metal salt and ammonium dinitramide into a solvent and mixing them uniformly at room temperature; the mixing time is preferably 5-60 minutes, preferably 5-30 minutes, for example 10 minutes, 15 minutes, 20 minutes or 30 minutes.

7. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: The soluble metal salt is copper nitrate trihydrate, and the nitrogen-containing ligand is one or more of ammonia, imidazole and 5-amino-1H-tetrazole; Preferably, the soluble metal salt is copper nitrate trihydrate, and the nitrogen-containing ligand is imidazole; Or, the soluble metal salt is cobalt nitrate hexahydrate, and the nitrogen-containing ligand is one or more of ammonia, imidazole and 5-amino-1H-tetrazole; Preferably, the soluble metal salt is cobalt nitrate trihydrate, and the nitrogen-containing ligand is 5-amino-1H-tetrazole.

8. The method for preparing the ADN-based metal ion nitrogen-containing complex energetic material according to claim 1, characterized in that: When the metal ion in the soluble metal salt is a divalent metal ion, the molar ratio of the metal ion in the soluble metal salt to the ammonium dinitramide is 1:(2-6), such as 1:2, 1:4 or 1:6; When the metal ion in the soluble metal salt is a trivalent metal ion, the molar ratio of the metal ion in the soluble metal salt to the ammonium dinitramide is 1:(3-9), for example 1:3; When the metal ion in the soluble metal salt is a divalent metal ion and the number of N atoms that can be coordinated in the nitrogen-containing ligand is 1, the molar ratio of the metal ion in the soluble metal salt to the nitrogen-containing ligand is 1:(4-12), for example, 1:4 or 1:8; When the metal ion in the soluble metal salt is a divalent metal ion and the number of N atoms that can be coordinated in the nitrogen-containing ligand is 2, the molar ratio of the metal ion in the soluble metal salt to the nitrogen-containing ligand is 1:(2-6), for example 1:2 or 1:

4.

9. An ADN-based metal nitrogen-containing complex energetic material prepared by the method for preparing an ADN-based metal ion nitrogen-containing complex energetic material as claimed in any one of claims 1 to 8.

10. Use of the ADN-based metal nitrogen-containing complex energetic material as claimed in claim 9 as a high-energy oxidant or a low-sensitivity burning rate catalyst in high-energy solid propellants.

Images