CuS nanostructure material, and preparation method and application thereof

Abstract

This invention discloses a CuS nanostructure material, its preparation method, and its applications. The CuS nanostructure material uses Cu-MOF octahedrons as a precursor, which are hydrothermally sulfided to obtain an octahedral hierarchical structure assembled from CuS nanorods. The CuS nanorods have a size of 50-100 nm, and the edge length of the precursor Cu-MOF octahedrons is 0.8-1 μm. This invention utilizes a one-step hydrothermal method to prepare a CuS nanostructure material through Cu-MOF sulfidation, resulting in a zinc-ion battery anode material with high conversion efficiency and excellent electrochemical performance.

Description

Technical Field

[0001] This invention belongs to the field of aqueous zinc-ion battery technology, specifically relating to a CuS nanostructure material, its preparation method, and its application. Background Technology

[0002] Aqueous zinc-ion batteries (ZIBs) are considered one of the most attractive alternative technologies for large-scale applications due to their low cost, environmental friendliness, and good ionic conductivity. However, zinc metal anodes, currently the most widely used type of ZIB, still suffer from some unavoidable problems, such as the easy formation of zinc dendrites, uncontrollable self-corrosion, and persistent gas evolution, leading to poor cycle stability, high charge overpotential, and low coulombic efficiency. Although many studies have proposed various strategies to improve the electrochemical performance of zinc metal anodes, including electrode structure design, surface modification, and zinc alloying, completely solving these problems remains extremely difficult. Therefore, exploring alternative zinc metal anode materials for zinc-ion batteries has become a top priority in overcoming major technical challenges in the field of zinc-ion batteries.

[0003] Zheng Cheng et al. invented a vanadium tetrasulfide anode material for zinc-ion batteries. However, the inherent poor conductivity and small specific surface area of ​​this vanadium tetrasulfide material severely hinder its application as an electrode material. Therefore, they had to combine this vanadium tetrasulfide material with conductive graphene to enhance its structure. (Guangdong University of Technology. Preparation method of zinc-ion battery anode and its active material, zinc-ion battery: CN202210453402.1[P]. 2022-08-02.) Summary of the Invention

[0004] In order to overcome the defects of the existing technology, the purpose of this invention is to provide a CuS nanostructure material, its preparation method and application. A CuS nanostructure material is prepared by sulfidation of Cu-MOF in one step hydrothermal method to obtain a zinc-ion battery anode material with efficient conversion reaction and excellent electrochemical performance.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A CuS nanostructure material, wherein the CuS nanostructure material is obtained by hydrothermal sulfurization of Cu-MOF octahedrons as precursors to obtain an octahedral hierarchical structure assembled from CuS nanorods, wherein the CuS nanorod structure has a size of 50-100 nm and the edge length of the precursor Cu-MOF octahedron is 0.8-1 μm.

[0007] A method for preparing CuS nanostructured materials includes the following steps;

[0008] a. Dissolve copper nitrate trihydrate (Cu(NO)3·3H2O) and polyvinylpyrrolidone (PVP) in anhydrous ethanol and stir until homogeneous to obtain solution A;

[0009] b. Dissolve 1,3,5-benzenetricarboxylic acid (H3BTC) in a certain amount of anhydrous methanol and stir until homogeneous to obtain solution B;

[0010] c. Slowly add solution B to solution A while stirring and continue stirring for a certain period of time. Then let it stand at room temperature for a certain period of time. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF.

[0011] d. Dissolve Cu-MOF and thioacetamide separately in ethylene glycol, sonicate for a certain time, mix the two solutions and stir evenly, then add hexadecyltrimethylammonium bromide, sonicate for a certain time, transfer the solution to a stainless steel reactor, react at a certain temperature, remove and wash with ethanol, and dry to obtain CuS nanostructure material.

[0012] In step a, the concentration of copper nitrate trihydrate is 70-100 mM; the mass of polyvinylpyrrolidone is 70-100 mM; and in step b, the concentration of 1,3,5-benzenetricarboxylic acid is 30-60 mM.

[0013] The ratio of copper nitrate trihydrate (Cu(NO)3·3H2O), polyvinylpyrrolidone (PVP), and 1,3,5-benzenetricarboxylic acid (H3BTC) is 2:1:1, which yields the most Cu-MOF product in the synthesis.

[0014] The settling time in step c is 28-48 hours; the stirring time in step c is 30 minutes.

[0015] In step d, the concentration of thioacetamide is 30-60 mM, and the concentration of hexadecyltrimethylammonium bromide is 5-30 mM.

[0016] In step d, the molar ratio of Cu-MOF to thioacetamide is 1:1 to 3. The main purpose is to enable thioacetamide to sulfide Cu-MOF into CuS product under hydrothermal conditions. The mass ratio of hexadecyltrimethylammonium bromide to thioacetamide is 0.5 to 2.5:1. The purpose of adding hexadecyltrimethylammonium bromide is mainly to intercalate hexadecyltrimethylammonium bromide molecules into the CuS crystal layer during CuS formation, which helps to increase the CuS interlayer spacing.

[0017] In step d, the reaction temperature is 80-160℃ and the reaction time is 10-16h.

[0018] In step d, the ultrasonic time is 30 minutes. The purpose of ultrasonication is to mix the solution more evenly.

[0019] The CuS nanostructure material is an octahedral hierarchical structure assembled from CuS nanorods, formed by hydrothermal sulfidation of Cu-MOF precursors (the octahedral structure is retained after hydrothermal treatment, but this octahedral structure is assembled from CuS nanorods). The CuS nanorod-assembled octahedral hierarchical structure material is used as the anode in an aqueous zinc-ion battery.

[0020] The beneficial effects of this invention are:

[0021] This invention cleverly combines transition metal sulfides with good kinetic properties and MOFs with huge specific surface area and high porosity to achieve a zinc-ion battery with excellent electrochemical performance and no zinc metal anode.

[0022] This invention uses MOFs with huge specific surface area and high porosity as precursors, and prepares transition metal sulfides with good kinetic performance through hydrothermal sulfidation. The MOF structure and transition metal sulfides are cleverly linked to realize a zinc-ion battery with excellent electrochemical performance and no zinc metal anode.

[0023] In this invention, the CuS nanostructure material is assembled from the precursor Cu-MOF and CuS nanorods. The huge specific surface area of ​​this structure is conducive to the insertion and extraction of zinc ions, which can improve the conversion rate of zinc-ion batteries.

[0024] In this invention, the CuS nanostructure material uses Cu-MOF as a precursor and is assembled from CuS nanorods into an octahedral hierarchical structure. It continues the octahedral structure of the Cu-MOF precursor and thus inherits the inherent advantage of the large specific surface area of ​​MOF materials, which is beneficial for the insertion and extraction of zinc ions and can improve the conversion rate of zinc-ion batteries. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the final product of the CuS nanostructured material of this invention. Detailed Implementation

[0026] The present invention will now be described in further detail with reference to the accompanying drawings.

[0027] Example 1

[0028] a. Dissolve 0.9 g of copper nitrate trihydrate (Cu(NO)3·3H2O) and 50 mL of polyvinylpyrrolidone (PVP) in a certain amount of anhydrous ethanol and stir until homogeneous to obtain solution A;

[0029] b. Dissolve 0.43 g of 1,3,5-benzenetricarboxylic acid (H3BTC) in 50 mL of anhydrous methanol and stir until homogeneous to obtain solution B;

[0030] c. Slowly add solution B to solution A while stirring and continue stirring for 30 min. Then let it stand at room temperature for 24 h. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF.

[0031] e. Dissolve 0.08 g of Cu-MOF and 0.18 g of thioacetamide separately in 20 mL of ethylene glycol. After sonicating for 30 min, mix the two solutions and stir evenly. Then add 0.1 g of hexadecyltrimethylammonium bromide and sonicate for 30 min. Transfer the solution to a stainless steel reactor and react at 80 °C for 10 h. Remove the reactor, wash with ethanol, and dry to obtain CuS nanostructured materials. Figure 1 As shown.

[0032] Example 2

[0033] a. Dissolve 0.9 g of copper nitrate trihydrate (Cu(NO)3·3H2O) and 50 mL of polyvinylpyrrolidone (PVP) in a certain amount of anhydrous ethanol and stir until homogeneous to obtain solution A;

[0034] b. Dissolve 0.43 g of 1,3,5-benzenetricarboxylic acid (H3BTC) in 50 mL of anhydrous methanol and stir until homogeneous to obtain solution B;

[0035] c. Slowly add solution B to solution A while stirring and continue stirring for 30 min. Then let it stand at room temperature for 24 h. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF.

[0036] e. Dissolve 0.08 g of Cu-MOF and 0.18 g of thioacetamide in 20 mL of ethylene glycol, respectively. After sonicating for 30 min, mix the two solutions and stir evenly. Then add 0.2 g of hexadecyltrimethylammonium bromide and sonicate for 30 min. Transfer the solution to a stainless steel reactor and react at 80 °C for 12 h. Remove the reactor, wash with ethanol, and dry to obtain CuS nanostructured materials.

[0037] Example 3

[0038] a. Dissolve 0.9 g of copper nitrate trihydrate (Cu(NO)3·3H2O) and 50 mL of polyvinylpyrrolidone (PVP) in a certain amount of anhydrous ethanol and stir until homogeneous to obtain solution A;

[0039] b. Dissolve 0.43 g of 1,3,5-benzenetricarboxylic acid (H3BTC) in 50 mL of anhydrous methanol and stir until homogeneous to obtain solution B;

[0040] c. Slowly add solution B to solution A while stirring and continue stirring for 30 min. Then let it stand at room temperature for 24 h. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF.

[0041] e. Dissolve 0.08 g of Cu-MOF and 0.18 g of thioacetamide in 20 mL of ethylene glycol, respectively. After sonicating for 30 min, mix the two solutions and stir evenly. Then add 0.3 g of hexadecyltrimethylammonium bromide and sonicate for 30 min. Transfer the solution to a stainless steel reactor and react at 80 °C for 16 h. Remove the reactor, wash with ethanol, and dry to obtain CuS nanostructured materials.

[0042] Example 4

[0043] a. Dissolve 0.9 g of copper nitrate trihydrate (Cu(NO)3·3H2O) and 50 mL of polyvinylpyrrolidone (PVP) in a certain amount of anhydrous ethanol and stir until homogeneous to obtain solution A;

[0044] b. Dissolve 0.43 g of 1,3,5-benzenetricarboxylic acid (H3BTC) in 50 mL of anhydrous methanol and stir until homogeneous to obtain solution B;

[0045] c. Slowly add solution B to solution A while stirring and continue stirring for 30 min. Then let it stand at room temperature for 24 h. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF.

[0046] e. Dissolve 0.08 g of Cu-MOF and 0.18 g of thioacetamide in 20 mL of ethylene glycol, respectively. After sonicating for 30 min, mix the two solutions and stir evenly. Then add 0.4 g of hexadecyltrimethylammonium bromide and sonicate for 30 min. Transfer the solution to a stainless steel reactor and react at 120 °C for 10 h. Remove the reactor, wash with ethanol, and dry to obtain CuS nanostructured materials.

[0047] Example 5

[0048] a. Dissolve 0.9 g of copper nitrate trihydrate (Cu(NO)3·3H2O) and 50 mL of polyvinylpyrrolidone (PVP) in a certain amount of anhydrous ethanol and stir until homogeneous to obtain solution A;

[0049] b. Dissolve 0.43 g of 1,3,5-benzenetricarboxylic acid (H3BTC) in 50 mL of anhydrous methanol and stir until homogeneous to obtain solution B;

[0050] c. Slowly add solution B to solution A while stirring and continue stirring for 30 min. Then let it stand at room temperature for 24 h. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF.

[0051] e. Dissolve 0.08 g of Cu-MOF and 0.18 g of thioacetamide in 20 mL of ethylene glycol, respectively. After sonicating for 30 min, mix the two solutions and stir evenly. Then add 0.4 g of hexadecyltrimethylammonium bromide and sonicate for 30 min. Transfer the solution to a stainless steel reactor and react at 120 °C for 12 h. Remove the reactor, wash with ethanol, and dry to obtain CuS nanostructured materials.

[0052] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing CuS nanostructured materials, characterized in that, Includes the following steps; a. Dissolve copper nitrate trihydrate and polyvinylpyrrolidone in anhydrous ethanol and stir until homogeneous to obtain solution A; b. Dissolve 1,3,5-benzenetricarboxylic acid in a certain amount of anhydrous methanol and stir until homogeneous to obtain solution B; c. Slowly add solution B to solution A while stirring and continue stirring for a certain period of time. Then let it stand at room temperature for a certain period of time. Wash the product with anhydrous methanol and then dry it to obtain Cu-MOF. d. Dissolve Cu-MOF and thioacetamide separately in ethylene glycol, sonicate for a certain time, mix the two solutions and stir evenly, then add hexadecyltrimethylammonium bromide, sonicate for a certain time, transfer the solution to a stainless steel reactor, react at a certain temperature, remove and wash with ethanol, dry to obtain CuS nanostructure material. In step d, the reaction temperature is 80-160 ℃ and the reaction time is 10-16 h; The CuS nanostructure material uses Cu-MOF octahedrons as precursors and undergoes hydrothermal sulfidation to obtain an octahedral hierarchical structure assembled from CuS nanorods. The CuS nanorod structure has a size of 50-100 nm, and the edge length of the precursor Cu-MOF octahedron is 0.8-1 μm.

2. The method for preparing CuS nanostructured materials according to claim 1, characterized in that, In step a, the concentration of copper nitrate trihydrate is 70-100 mM; in step b, the concentration of 1,3,5-benzenetricarboxylic acid is 30-60 mM.

3. The method for preparing CuS nanostructured materials according to claim 1, characterized in that, The ratio of copper nitrate trihydrate, polyvinylpyrrolidone, and 1,3,5-benzenetricarboxylic acid is 2:1:

1.

4. The method for preparing CuS nanostructured materials according to claim 1, characterized in that, The settling time in step c is 28-48 h; the stirring time in step c is 30 min.

5. The method for preparing CuS nanostructured material according to claim 1, characterized in that, In step d, the concentration of thioacetamide is 30-60 mM, and the concentration of hexadecyltrimethylammonium bromide is 5-30 mM.

6. The method for preparing CuS nanostructured material according to claim 1, characterized in that, In step d, the molar ratio of Cu-MOF to thioacetamide is 1:1~3, and the mass ratio of hexadecyltrimethylammonium bromide to thioacetamide is 0.5~2.5:

1.

7. The method for preparing CuS nanostructured material according to claim 1, characterized in that, In step d, the sonication time is 30 minutes. The purpose of sonication is to mix the solution more evenly.

8. The CuS nanostructured material obtained by the preparation method according to any one of claims 1-7, characterized in that, CuS nanostructured materials are octahedral hierarchical structures assembled from CuS nanorods, formed by hydrothermal sulfidation of Cu-MOF precursors. These CuS nanorod-assembled octahedral hierarchical structure materials are used as anodes in aqueous zinc-ion batteries.

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