An organic small molecule-based superlattice copper selenide composite material and preparation and application thereof

Abstract

The application discloses an organic small-molecule-based superlattice copper selenide composite material and a preparation and application thereof, and belongs to the field of new materials and electrochemistry technology. The application takes aliphatic amine organic small molecules such as diethylenetriamine as a morphology control and superlattice intercalation molecule, utilizes hydration electrons generated by water radiolysis to reduce sodium selenosulfite and copper ions in a precursor solution, and synthesizes the organic small-molecule-based superlattice copper selenide composite material. The composite material has a nanosheet structure, excellent conductivity and reversible zinc storage capacity, and exhibits excellent rate performance and cycle stability as an electrode material of a water-based zinc ion battery. Moreover, the preparation method of one-step radiation reduction has mild conditions, is flexible and controllable, has low energy consumption and small environmental pollution, is favorable for the design of atomic-level defects and weakening of the damage to the structure and morphology of copper selenide in the preparation process.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new materials and electrochemistry, and particularly relates to an organic small molecule-based superlattice copper selenide composite material and a preparation method and application thereof. BACKGROUND

[0002] As a new type of green electrochemical secondary energy storage device, aqueous zinc-ion batteries have become a research hotspot to replace traditional organic lithium-ion batteries in large-scale power devices and wearable electronic devices due to their low cost, excellent safety and biocompatibility. However, the corrosion, passivation and hydrogen evolution problems of high-activity zinc metal negative electrode in weak acid aqueous electrolyte seriously limit the cycle stability of the battery and reduce its durability in practical application systems. At the same time, the continuous uneven stripping / deposition of zinc ions on the negative electrode surface can easily cause dendrite growth and cause short circuits, further shortening the service life of the aqueous zinc-ion battery. Although metal surface coating modification, electrolyte optimization and electrode structure design can alleviate the occurrence of side reactions at the electrode and solution interface, they cannot fundamentally solve the problem of high activity of zinc metal. Therefore, it is necessary to develop high-stability alternative negative electrode materials with excellent zinc storage capacity to solve the great challenges faced by aqueous batteries. At present, elemental and transition metal compound type negative electrodes mainly based on sulfur family elements (S, Se and Te) have attracted widespread attention due to their rich resources, easy-to-adjust structure composition and multi-electron redox energy storage mechanism. Among them, zincophilic transition metal selenides have the conductivity of metal and high theoretical capacity, and can maintain high coulombic efficiency during long cycle tests, and can reversibly store zinc ions in a conversion-type reaction to the greatest extent. Compared with the structural collapse caused by the rapid insertion / deintercalation of zinc ions in the intercalation process, transition metal selenide can maintain the integrity of the structure during repeated charge and discharge cycles through solid-solid conversion reaction. However, due to the slow zinc ion diffusion dynamics in the material bulk phase, the electrochemical performance of transition metal selenide negative electrode is generally limited by the insufficient reversible capacity release at high current density, which leads to the imbalance of the proportion of positive and negative electrode materials in aqueous zinc-ion batteries, and the overall power density is low. Therefore, the development of new high-energy transition metal compound negative electrode materials through crystal structure optimization and design to reduce the zinc ion diffusion barrier and improve the rate performance is the key to realizing high-power practical zinc-ion batteries.

[0003] Li et al. (J. Li., ACS Nano 2023, 17, 18507-18516.) prepared a non-stoichiometric cubic phase copper selenide material by chemical precipitation method, which confirmed its great potential as a metal-free negative electrode for aqueous zinc-ion batteries. The cubic phase copper selenide material can exhibit excellent zinc storage behavior under high area loading conditions, and still has a capacity of 3.1 mAh cm -2high reversible capacity. However, the zinc ion migration rate of the copper selenide bulk phase material without morphology regulation and crystal structure modification is still too low, and the capacity retention rate at different rates cannot adapt to the positive electrode material. Li Qingwen et al. (CN118026152A) synthesized a one-dimensional carbon-coated copper selenide nanowire coaxial heterostructure material by chemical vapor deposition method. The specific surface area of the material is increased and the ion diffusion path is effectively shortened through one-dimensional structure design, and the external carbon layer and the heterostructure cooperatively improve the transmission rate of the electrode surface electrons, thereby improving the rate performance and stability of copper selenide. However, the high temperature and too complex material synthesis steps are not conducive to the green batch preparation of the electrode in the actual system. Cui Fuhan et al. (CN117855469A) prepared a new type of high-activity nanoscale ruthenium selenide negative electrode material, which can be compatible with a wide pH electrolyte system from alkaline to acidic. The water-based zinc ion full battery assembled by the ruthenium selenide and manganese dioxide exhibits a reversible capacity of 147 mAh g -1 and can be stably operated for 100 cycles. However, due to the heavy atomic mass of ruthenium atoms, the theoretical specific capacity thereof is insufficient to achieve sufficient zinc storage behavior at a large current density. Meanwhile, under the limitation of a higher zinc ion diffusion barrier, frequent charge and discharge behavior can cause the crushing and pulverization of the electrode, resulting in rapid decay of the reversible capacity and poor cycle stability. SUMMARY

[0004] The purpose of the present application is to develop a transition metal selenide composite material with excellent rate performance, long cycle service life and low cost, in order to solve the problems of low reversible capacity, slow zinc ion diffusion kinetics, poor structural stability, high energy consumption of the preparation method, and complicated process of the current metal-free based negative electrode.

[0005] To achieve the above-mentioned purpose, the technical solutions adopted by the present application are as follows:

[0006] In the first aspect of the present application, an organic small molecule-based superlattice copper selenide composite material is provided, in which an organic small molecule is inserted into a copper selenide bulk phase lattice to form a superlattice structure, wherein the molecular formula of the copper selenide is Cu 2-x Se, 0.01≤x≤0.4; the organic small molecule is an aliphatic amine organic small molecule, and the mass content of the organic small molecule in the composite material is 0.1%-10%.

[0007] In the organic small molecule-based superlattice copper selenide composite material of the present application, the superlattice intercalation of the organic small molecule effectively modulates the electronic structure of the cubic phase copper selenide, and improves the charge density of the Cu and Se sites.

[0008] In the present application, when the organic small molecule is diethylenetriamine (DETA), the composite material is denoted as Cu 2- xSe-DETA.

[0009] Preferably, the organic small molecule based superlattice copper selenide composite material of the present application is in a two-dimensional nanosheet structure. In some embodiments of the present application, the composite material is assembled into a flower-shaped microspherical morphology with a thickness of 2-5 nm.

[0010] Further, in the above organic small molecule based superlattice copper selenide composite material, preferably 0.05≤x≤0.3.

[0011] Further, the above organic small molecule based superlattice copper selenide composite material is prepared by a one-step radiation reduction method. Under the regulation of organic small molecules, the hydrated electrons generated by water radiation reduce the sodium selenosulfite and copper ions in the precursor solution, and the two combine to obtain the organic small molecule based superlattice copper selenide composite material.

[0012] In the second aspect of the present application, a preparation method of the above organic small molecule based superlattice copper selenide composite material is provided, comprising the following steps:

[0013] 1) First, prepare a copper precursor aqueous solution, and add a certain volume of organic small molecule solvent to it;

[0014] 2) Add a certain amount of sodium selenosulfite solution to the above mixed solution, and after adding a free radical scavenger, introduce inert gas and seal, and perform radiation reduction reaction using γ-rays or electron beams;

[0015] 3) The solid obtained by radiation reduction reaction is subjected to suction filtration, washing, and vacuum drying to obtain the organic small molecule based superlattice copper selenide composite material.

[0016] In the above step 1), the copper precursor is a copper salt, which can be selected from one or more of copper nitrate, copper sulfate, copper chloride, and copper acetate.

[0017] In the above step 1), the organic small molecule is selected from one or more of diethylene triamine, ethylene diamine, triethylene tetramine, tetraethylene pentamine, ethylene diamine tetraacetic acid, and other aliphatic amine small molecules with multiple amine sites.

[0018] In the above step 2), the free radical scavenger is an alcohol organic solvent, which can be selected from one or more of n-propanol, isopropanol, tert-butyl alcohol, ethylene glycol, and glycerol.

[0019] In the above step 2), the inert gas can be nitrogen, argon, or a mixture thereof, and the gas introduction time is 1-30 min.

[0020] In the above step 2), if γ-ray irradiation is selected, the sample is placed in an irradiation tube and sealed with inert gas, and the irradiation is performed using a60 The irradiation reduction reaction is carried out by Co-generated γ-rays. Preferably, the irradiation is carried out at room temperature, with a dose rate of 50-400 Gy / min and an absorbed dose of 20-400 kGy.

[0021] In the above step 2), if electron beam irradiation is selected, the sample is injected into a plastic bag and sealed with inert gas, and the irradiation reduction reaction is carried out at room temperature using an electron accelerator irradiation device. The energy of the electron accelerator is preferably 0.1-20 MeV, the dose rate of electron beam irradiation is 2-50 kGy / pass, and the absorbed dose is 50-500 kGy.

[0022] In some embodiments of the present application, the concentration of copper ions in the irradiated sample is 2-100 mmol / L, preferably 4-50 mmol / L, and more preferably 8-40 mmol / L.

[0023] In some embodiments of the present application, the organic small molecule is diethylenetriamine, and the amount of diethylenetriamine added to the irradiated sample is 0.2-15 mL, preferably 0.4-10 mL, and more preferably 0.6-5 mL for a 28 mL irradiated sample.

[0024] In some embodiments of the present application, the concentration of sodium selenosulfite solution in the irradiated sample is 2-200 mmol / L, preferably 5-100 mmol / L, and more preferably 10-50 mmol / L.

[0025] In some embodiments of the present application, the concentration of the free radical scavenger in the irradiated sample is 10-500 mL / L, preferably 50-400 mL / L, and more preferably 100-300 mL / L.

[0026] In a third aspect of the present application, the use of the above-mentioned organic small molecule-based superlattice copper selenide composite material as an electrode material in a water-based zinc ion battery is provided. The water-based zinc ion battery can be a button cell, a flexible pouch cell, a flexible fiber cell, and a non-flexible pouch cell, etc.

[0027] In some embodiments of the present application, a button cell device is provided, which comprises an electrode material as described above, such as Cu 2-x Se-DETA. It should be noted that for the button cell device provided by the present application, in addition to the electrode material using the electrode material provided by the present application, other components required for the button cell device, such as current collector, battery shell, spring, gasket, electrolyte, zinc foil, and separator, etc. can be realized by using the related technical solutions in the prior art, and the present application does not limit them.

[0028] In some embodiments of the present application, a flexible pouch battery device is provided, which comprises an electrode material as described above, such as Cu 2-x Se-DETA. It should be noted that for the flexible pouch full battery device provided by the present application, in addition to the electrode material using the electrode material provided by the present application, other components required for the flexible pouch full battery device, such as plastic packaging machine, graphite foil, manganese dioxide, gel electrolyte, diaphragm, etc. can be realized by using the related technical solutions in the prior art, and the present application does not limit it here.

[0029] The present application also provides an electric device product, which comprises a battery device such as a flexible pouch battery as described above. It should be noted that other parts of the device product in addition to the above device can be realized by using the related technical solutions in the prior art, and the present application does not limit it here. The electric device product is preferably a flexible display screen, a fan, a mobile phone, etc.

[0030] Compared with the prior art, the present application has the following technical advantages:

[0031] (1) The present application uses organic small molecules such as diethylene triamine as morphology control and superlattice intercalated organic molecules, and synthesizes superlattice copper selenide composite materials based on organic small molecules by using radiation reduction method. The composite material has a nanosheet structure accessible to zinc ions, which increases the contact area with the electrolyte, thereby promoting the improvement of reversible capacity. At the same time, the organic small molecules such as DETA are inserted into the crystal lattice of copper selenide to form a superlattice structure, which weakens the migration barrier of zinc ions and improves the ion diffusion dynamics, effectively improving the rate performance and structural stability of the material. The lattice stress induced by the charge repulsion effect of DETA molecules through N atoms to Cu and Se sites further adjusts the electrochemical properties of copper selenide. Therefore, the Cu 2-x Se-DETA has excellent electrical conductivity and reversible zinc storage capacity, and can exhibit high rate capacity retention at high current density.

[0032] (2) The superlattice copper selenide based on organic small molecules synthesized by the present application has excellent rate performance and cycle stability as a negative electrode material for aqueous zinc ion battery. The assembled flexible pouch full battery can withstand a wide working temperature of-20℃ to 40℃, and can stably operate under a bending working condition of 0°-180°, and has excellent durability and robustness.

[0033] (3) Compared with conventional inorganic nanoparticle synthesis strategies such as hydrothermal method, electrodeposition method and microwave-assisted method, the use of ionizing radiation method to synthesize organic small molecule superlattice copper selenide composite material is green, mild, flexible and controllable, low in energy consumption and small in environmental pollution, which is conducive to the design of atomic-level defects and the weakening of the damage to the structure and morphology of transition metal selenide in the preparation process. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The preparation process and structural schematic diagram of the copper selenide composite material based on the superlattice of diethylenetriamine molecules.

[0035] Figure 2 X-ray diffraction (XRD) spectrum of the Cu 2-x Se-DETA composite material prepared in Example 1.

[0036] Figure 3A Scanning electron microscope (SEM) image of the Cu 2-x Se-DETA composite material prepared in Example 1.

[0037] Figure 3B Transmission electron microscope (TEM) image of the Cu 2-x Se-DETA composite material prepared in Example 1.

[0038] Figure 4A X-ray photoelectron spectroscopy (XPS) image of the Cu 2-x Se-DETA composite material prepared in Example 1.

[0039] Figure 4B High-resolution XPS image of Cu in the Cu 2-x Se-DETA composite material prepared in Example 1.

[0040] Figure 4C High-resolution XPS image of Se in the Cu 2-x Se-DETA composite material prepared in Example 1.

[0041] Figure 5A Rate performance graph of the Cu 2-x Se-DETA in aqueous zinc ion button cell.

[0042] Figure 5B Cycle stability test graph of the Cu 2-x Se-DETA in button cell under 5Ag -1 Current density.

[0043] Figure 6A Constant current charge-discharge curve of the Cu 2-x Se-DETA assembled into flexible soft pack battery at different temperatures.

[0044] Figure 6B .Cu 2-x Cyclic stability test results of Se-DETA assembled flexible pouch cells under different bending conditions. Detailed Implementation

[0045] The present invention will be further illustrated in detail below through embodiments, but the scope of the invention is not limited in any way.

[0046] Example 1

[0047] Dissolve 200 mg of copper acetate in deionized water containing 3.2 mL of DETA to prepare a 12 mL aqueous solution. Then, add 2 mL of 0.25 M sodium selenite solution, 8 mL of isopropanol, and 6 mL of deionized water to the above solution and mix thoroughly. Continuously bubble N2 into the mixture to remove air from the system, then seal before use. 60 A Co radioactive source was used for gamma-ray irradiation at a dose rate of 100 Gy / min, with an absorbed dose of 100 kGy. After the irradiation reaction, the solid was collected by filtration, washed three times with deionized water and ethanol, and then dried in a vacuum oven at 60°C for 24 hours to finally obtain Cu. 2-x Se-DETA, x = 0.2.

[0048] Cu 2-x The XRD, SEM, TEM, and XPS images of the Se-DETA composite material are shown below. Figure 2 , Figure 3A , Figure 3B and Figures 4A to 4C As shown, the superlattice-modified copper selenide prepared by radiation reduction exhibits a cubic phase copper selenide structure, with two-dimensional nanosheets of 2-5 nm thickness assembled into flower-like microspheres. Figures 4A to 4C This indicates that the superlattice structure achieved by DETA molecular intercalation based on radiation method effectively modulates the electronic structure of copper selenide and increases the charge density of Cu and Se sites.

[0049] Cu 2-x Se-DETA, polyvinylidene fluoride (PVDF), and conductive carbon black were dispersed in N-methylpyrrolidone (NMP) in a 7:2:1 ratio to prepare an electrode paste. The paste was uniformly coated onto a titanium foil surface and then dried in a vacuum oven at 60°C for 24 hours. The resulting Cu... 2-x Se-DETA electrode sheets were cut to the appropriate size and assembled with zinc foil to form button cells. 2M zinc sulfate (ZnSO4) was used as the electrolyte, and a glass fiber separator was used. The assembled button cells were subjected to constant current charge-discharge tests on a Blue Battery testing system to study their rate performance and cycle stability.

[0050] Using the above method with Cu 2-x Aqueous zinc-ion coin cells assembled using Se-DETA as electrode material exhibit electrochemical performance such as... Figure 5A , Figure 5B As shown. In 5Ag -1 At current density, Cu 2-x Se-DETA exhibits a capacity of 154.6 mAh g. -1 The specific capacity retains 98.6% after 10,000 cycles.

[0051] Cu 2-x Se-DETA material was used as the negative electrode, manganese dioxide as the positive electrode, and a polyacrylamide gel electrolyte containing 2M ZnSO4 was assembled into a flexible pouch battery. The electrochemical activity and durability of the full cell were tested. Figure 6A , 6B As shown. Cu 2-x Se-DETA can operate normally in a wide temperature range of -20°C to 40°C and maintains excellent cycle stability under bending conditions of varying degrees from 0° to 180°.

[0052] Example 2

[0053] The amount of diethylenetriamine used in Example 1 was changed to 0.8 mL, while other preparation conditions remained the same as in Example 1. The amount of DETA affected the degree of superlattice formation of copper selenide, thus altering its electrochemical zinc storage capacity. Its rate performance and cycle stability in the assembled button cell were significantly reduced compared to Example 1. At 5 Ag... -1 At current density, it has 76.3 mAh g. -1 The reversible specific capacity retains 85.9% of its capacity after 10,000 cycles.

[0054] Example 3

[0055] The amount of diethylenetriamine used in Example 1 was changed to 1.2 mL, while other preparation conditions remained the same as in Example 1. The rate performance and cycle stability of the assembled button cell were lower compared to Example 1. At 5 Ag... -1 At current density, it has 97.5 mAh g. -1 The reversible specific capacity has a capacity retention rate of 87.5% after 10,000 cycles.

[0056] Example 4

[0057] The amount of diethylenetriamine used in Example 1 was changed to 2.4 mL, while other preparation conditions remained the same as in Example 1. The rate performance and cycle stability of the assembled button cell were lower compared to Example 1. At 5 Ag... -1 At current density, it has 116.3 mAh g.-1 The reversible specific capacity retains 90.2% of its capacity after 10,000 cycles.

[0058] Example 5

[0059] The amount of diethylenetriamine used in Example 1 was changed to 2.8 mL, while other preparation conditions remained the same as in Example 1. The rate performance and cycle stability of the assembled button cell were slightly lower compared to Example 1. At 5 Ag... -1 At current density, it has 134.1 mAh g. -1 The reversible specific capacity retains 92.4% of its capacity after 10,000 cycles.

[0060] Example 6

[0061] The radiation reduction dose rate in Example 1 was changed to 50 Gy / min, while other preparation conditions remained the same as in Example 1. This dose rate adjustment altered the morphology and superlattice degree of the copper selenide material, thus affecting its electrochemical activity. Its performance in a coin cell assembly was slightly lower than that in Example 1. At 5 Ag... -1 At current density, it has 126.8 mAh g. -1 The reversible specific capacity retains 93.3% of its capacity after 10,000 cycles.

[0062] Example 7

[0063] The radiation reduction dose rate in Example 1 was changed to 70 Gy / min, while other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that in Example 1. At 5 Ag... -1 At current density, it has 131.7 mAh g. -1 The reversible specific capacity retains 94.5% of its capacity after 10,000 cycles.

[0064] Example 8

[0065] The radiation reduction dose rate in Example 1 was changed to 150 Gy / min, while other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that in Example 1. At 5 Ag... -1 At current density, it has 122.9 mAh g. -1 The reversible specific capacity retains 92.8% of its capacity after 10,000 cycles.

[0066] Example 9

[0067] The radiation reduction dose rate in Example 1 was changed to 200 Gy / min, while other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that in Example 1. At 5 Ag... -1At current density, it has 105.5 mAh g. -1 The reversible specific capacity retains 91.3% of its capacity after 10,000 cycles.

[0068] Example 10

[0069] In Example 1, γ-irradiation was replaced with electron beam irradiation, with an absorbed dose of 100 kGy and a dose rate of 20 kGy / pass. Other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that of Example 1. At 5Ag... -1 At current density, it has 145.2 mAh g. -1 The reversible specific capacity retains 95.2% of its capacity after 10,000 cycles.

[0070] Example 11

[0071] The γ-irradiation absorbed dose in Example 1 was changed to 30 kGy, while other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that in Example 1. At 5 Ag... -1 At current density, it has 84.7 mAh g. -1 The reversible specific capacity retains 90.7% of its capacity after 10,000 cycles.

[0072] Example 12

[0073] The γ-irradiation absorbed dose in Example 1 was changed to 70 kGy, while other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that in Example 1. At 5Ag... -1 At current density, it has 107.3 mAh g. -1 The reversible specific capacity retains 95.9% of its capacity after 10,000 cycles.

[0074] Example 13

[0075] The γ-irradiation absorbed dose in Example 1 was changed to 150 kGy, while other preparation conditions remained the same as in Example 1. The performance of this assembly in a button cell was slightly lower than that in Example 1. At 5Ag... -1 At current density, it has 148.1 mAh g. -1 The reversible specific capacity retains 96.3% of its capacity after 10,000 cycles.

[0076] Example 14

[0077] In Example 1, copper chloride was used as the copper precursor, and other preparation conditions were the same as in Example 1. The performance of the assembled button cell was slightly lower than that of Example 1. At 5Ag... -1 At current density, it has 135.7 mAh g.-1 a reversible specific capacity of 141.8 mAh g-1, and a capacity retention of 90.9% after 10,000 cycles.

[0078] Example 15

[0079] The copper precursor in Example 1 was replaced by copper sulfate, and other preparation conditions were the same as Example 1. Its performance in the assembled button cell was slightly lower than that of Example 1. It had a reversible specific capacity of 92.7 mAh g-1at a current density of 5 Ag-1, and a capacity retention of 87.2% after 10,000 cycles. -1 -1 a reversible specific capacity of 141.8 mAh g-1, and a capacity retention of 90.9% after 10,000 cycles.

[0080] Example 16

[0081] The diethylenetriamine in Example 1 was replaced by ethylenediamine, and other preparation conditions were the same as Example 1. Its performance in the assembled button cell was slightly lower than that of Example 1. It had a reversible specific capacity of 92.7 mAh g-1at a current density of 5 Ag-1, and a capacity retention of 87.2% after 10,000 cycles. -1 -1 a reversible specific capacity of 141.8 mAh g-1, and a capacity retention of 90.9% after 10,000 cycles.

[0082] Example 17

[0083] The diethylenetriamine in Example 1 was replaced by triethylenetetramine, and other preparation conditions were the same as Example 1. Its performance in the assembled button cell was slightly lower than that of Example 1. It had a reversible specific capacity of 99.2 mAh g-1at a current density of 5 Ag-1, and a capacity retention of 88.5% after 10,000 cycles. -1 -1 a reversible specific capacity of 141.8 mAh g-1, and a capacity retention of 90.9% after 10,000 cycles.​​​

Claims

1. A superlattice-structured copper selenide composite material based on organic small molecules, characterized in that, Organic small molecules are inserted into the bulk lattice of copper selenide to form a superlattice structure, wherein the molecular formula of copper selenide is Cu. 2-x Se, 0.01 ≤ x ≤ 0.4; the organic small molecule is an aliphatic amine molecule, and its mass content in the composite material is 0.1%-10%; the composite material is a two-dimensional nanosheet structure, which is assembled into a flower-like microsphere morphology by two-dimensional nanosheets with a thickness of 2-5 nm.

2. The superlattice-structured copper selenide composite material as described in claim 1, characterized in that, The organic small molecule is selected from one or more of diethylenetriamine, ethylenediamine, triethylenetetraamine, tetraethylenepentamine, and ethylenediaminetetraacetic acid.

3. The superlattice-structured copper selenide composite material as described in claim 1, characterized in that, 0.05 ≤ x ≤ 0.3。 4. The method for preparing the superlattice-based copper selenide composite material based on organic small molecules according to any one of claims 1 to 3, comprising the following steps: 1) Prepare an aqueous solution of copper precursor and add an organic small molecule solvent, wherein the organic small molecule is an aliphatic amine molecule; 2) Add sodium selenosulfite solution and free radical scavenger to the mixed solution obtained in step 1), then pass in an inert gas and seal it, and carry out a radiation reduction reaction by irradiation with gamma rays or electron beams; 3) The solid obtained from the radiation reduction reaction is filtered, washed, and vacuum dried to obtain the superlattice copper selenide composite material based on organic small molecules.

5. The preparation method according to claim 4, characterized in that, The copper precursor mentioned in step 1) is a copper salt, selected from one or more of copper nitrate, copper sulfate, copper chloride, and copper acetate; the free radical scavenger mentioned in step 2) is an alcoholic organic solvent, selected from one or more of n-propanol, isopropanol, tert-butanol, ethylene glycol, and glycerol; step 2) uses gamma-ray irradiation at a dose rate of 50-400 Gy / min and an absorbed dose of 20-400 kGy; Alternatively, electron beam irradiation can be used, with a dose rate of 2 to 50 kGy / pass and an absorbed dose of 50 to 500 kGy.

6. The preparation method according to claim 4, characterized in that, Step 2) The concentration of copper ions in the irradiated sample is 2~100 mmol / L, and the concentration of sodium selenite solution is 2~200 mmol / L.

7. The application of the superlattice-based copper selenide composite material based on organic small molecules as an electrode material in aqueous zinc-ion batteries, according to any one of claims 1 to 3.

8. An aqueous zinc-ion battery device comprising the superlattice copper selenide composite material based on organic small molecules as described in any one of claims 1 to 3, including a button cell, a flexible pouch cell, a flexible fibrous cell, and a non-flexible pouch cell.

9. An electric device product comprising the aqueous zinc-ion battery device of claim 8.

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