Preparation method of (Co, Cu, M1) 9S8 nanoparticle-induced composite vacancy-rich Ov-CoCuM1-LDH electrode material and application of (Co, Cu, M1) 9S8 nanoparticle-induced composite vacancy-rich Ov-CoCuM1-LDH electrode material in hybrid supercapacitor

Abstract

The invention belongs to the technical field of composite electrode materials, and relates to a preparation method of a (Co, Cu, M1) 9S8 nanoparticle-induced composite vacancy-rich Ov-CoCuM1-LDH electrode material, which comprises the following steps: preparing a Cu (OH) 2 nanowire / CF precursor by using an in-situ oxidation self-assembly method, obtaining a nanosheet cross-linked hollow nanorod CoCuM1-LDH (M1 = Ni, Fe) / CF intermediate by further improving ZIFs and a Lewis acid exchange / etching method, and preparing the (Co, Cu, M1) 9S8 nanoparticle-induced composite vacancy-rich Ov-CoCuM1-LDH / CF electrode material. And then preparing high-performance (Co, Cu, M1) 9S8 (M1 = Ni, Fe) nano-particle induced composite rich vacancy Ov-CoCuM1-LDH / CF positive and negative electrodes by a controllable solvothermal method. According to the CoCuM1-LDH composite material, the foam copper CF and Cu (OH) 2 derived nanosheet cross-linked hollow nanorod hierarchical structure provides a stable substrate and increases the conductivity and specific surface area of the material, and (Co, Cu, M1) 9S8 (M1 = Ni, Fe) nanoparticles, Ov and the like are compounded and intercalated into CoCuM1-LDH, so that the electronic structure is adjusted, an intermediate buffer effect is achieved, LDH volume expansion is prevented, and the structure is more stable; when the prepared electrode material is applied to a hybrid supercapacitor, the use of an adhesive is avoided, the impedance is reduced, and the electrochemical performance is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite electrodes, and relates to a high-capacity electrode, in particular to a (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v -Preparation method of CoCuM1-LDH electrode material and its application in hybrid supercapacitors. Background Art

[0002] Due to the limitation of electrode capacity, especially negative electrode capacity, the energy density of supercapacitors (10-50 Wh kg -1 ) development is significantly limited. For example, currently commercial supercapacitors using activated carbon as anodes have extremely limited energy density. The development of high-capacity and highly active electrodes, especially high-capacity anodes, is a critical and pressing issue. In recent years, Ni-based cathodes developed using Ni-based LDHs and Fe-based anodes developed using Fe-based LDHs have gained recognition among researchers. However, their high internal resistance and potential volume expansion present significant obstacles to their further development.

[0003] This paper proposes a dual synergistic mechanism for hybrid supercapacitors (HSCs): developing a high-performance Ni / Fe-based positive / negative electrode (0-3 valence) construction strategy through multi-valence, multi-level structure, high entropy, and heterogeneous structure to form a negative / positive electrode with synergistic coupling of battery-type and capacitor-type energy storage, thereby breaking through the limitations of traditional electrode single energy storage, and achieving a theoretical capacity of 2-5 times that of conventional capacitors. Developing highly active (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles to induce composite vacancy-rich layered double hydroxide O v - A method for preparing high-capacity and high-activity positive and negative electrodes using CoCuM1-LDH, pushing the energy density of laboratory HSCs beyond 100 Wh kg -1 This technological breakthrough enables HSCs to evolve from auxiliary energy storage to core energy storage, providing high-security solutions for new energy vehicles and smart grids. Summary of the Invention

[0004] In view of the above-mentioned deficiencies in the prior art, the present invention aims to disclose a (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v -Preparation method of CoCuM1-LDH electrode material and its application in hybrid supercapacitors.

[0005] Technical Solution

[0006] Using copper foam, oxidant, alkali source, cobalt salt, nickel salt, iron salt organic framework molecule (2-methylimidazole, 2-MI), and sulfur source as raw materials, the Cu(OH)2 nanowire / CF (copper foam) precursor was first prepared by in situ oxidative self-assembly method. Then, the nanosheet-crosslinked hollow nanocolumns CoCuM1-LDH (M1=Ni, Fe) / CF intermediate were obtained by a one-step modified ZIFs (zeolite imidazole framework) and Lewis acid exchange / etching method. Then, high-performance (Co, Cu, M1)9S8 (M1=Ni, Fe) nanoparticles were prepared by a controllable solvothermal method to induce composite vacancy-rich O v -CoCuM1-LDH / CF positive and negative electrodes, and finally a high energy density hybrid supercapacitor (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) / / (-)(Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF.

[0007] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0008] A. Immerse the copper foam (CF) in a deionized water solution containing an oxidant and an alkali source for in-situ oxidation self-assembly reaction for 1 to 30 minutes, preferably 20 minutes, and then wash and dry to obtain a nanorod array electrode Cu(OH)2 / CF;

[0009] B. Immerse the nanopillar array electrode Cu(OH)2 / CF in a methanol solution containing a cobalt source, a nickel source, and a 2-MI solution, transfer it into a reactor, and react at 100-140°C for 4-8 hours, preferably at 120°C for 6 hours. After cooling naturally to room temperature, take it out, wash it with deionized water and anhydrous ethanol several times, and dry it at 60°C to obtain a columnar hierarchical structure CoCuNi-LDH / CF cross-linked with 2-MI intercalated and substituted layered double hydroxide nanosheets;

[0010] C. Immerse the nanopillar array electrode Cu(OH)2 / CF in a methanol solution containing a cobalt source, an iron source, and a 2-MI solution, move it into a reactor, and react at 100-140°C for 4-8 h, preferably at 120°C for 6 h. After cooling naturally to room temperature, take it out, wash it with deionized water and anhydrous ethanol several times, and dry it at 60°C to obtain a columnar hierarchical structure CoCuFe-LDH / CF with 2-MI intercalated and substituted layered double hydroxide nanosheets cross-linked with ZIFs polyhedrons;

[0011] D. The cross-linked columnar hierarchical structure CoCuM1-LDH (M1 = Ni, Fe) / CF prepared in steps B and C was mixed with an ethanol solution containing a sulfur source and reacted in an autoclave at 100-140°C for 1-3 hours, preferably at 120°C for 2 hours. The obtained product was washed with deionized water and ethanol, and dried to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles induced composite vacancy-rich O v -CoCuM1-LDH positive electrode material (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and negative electrode material (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0012] In a preferred embodiment of the present invention, in step A, the material ratio of copper foam (CF), oxidant, alkali source, and deionized water is 1-3 cm 2 : 0.3~0.6g: 1~3g: 10~30mL, preferably 2cm 2 : 0.45g: 2g: 20mL, wherein the oxidant is ammonium persulfate or sodium persulfate, preferably ammonium persulfate; the alkali source is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.

[0013] In a preferred embodiment of the present invention, in step B, the material ratio of cobalt source, nickel source, 2-MI and methanol is 100~300mg:100~300mg:300~500mg:10~30mL, preferably 150mg:150mg:300mg:20mL; wherein the cobalt source is Co(NO3)2 or CoCl2, preferably Co(NO3)2, and the nickel source is Ni(NO3)2 or NiCl2, preferably Ni(NO3)2.

[0014] In a preferred embodiment of the present invention, in step C, the material ratio of cobalt source, iron source, 2-MI and methanol is 50~150mg:50~150mg:100~300mg:10~30mL, preferably 100mg:100mg:200mg:20mL; wherein the cobalt source is Co(NO3)2 or CoCl2, preferably Co(NO3)2, and the iron source is Fe(NO3)2 or FeCl2, preferably Fe(NO3)2.

[0015] In a preferred embodiment of the present invention, in step D, the material ratio of the nanosheet cross-linked columnar hierarchical structure CoCuM1-LDH (M1=Ni,Fe) / CF, sulfur source, and ethanol solution is 1~3cm 2 : 0.5~1.5mg: 10-30mL, preferably 2cm 2: 1.0 mg: 20 mL; wherein the sulfur source is thioacetamide (TAA) or sodium sulfide (Na2S), preferably TAA.

[0016] According to the method of the present invention, the prepared (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles induce composite vacancy-rich O v -CoCuM1-LDH positive electrode material (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and negative electrode material (Co, Cu, Fe)9S8@O v The size of -CoCuFe-LDH / CF(-) can be manipulated by cutting, bending, etc. according to actual conditions. In its microscopic state, (Co, Cu, M1)9S8 (M1=Ni, Fe) nanoparticles and vacancy-rich O v -CoCuM1-LDH nanosheets are cross-linked to form hollow nanocolumns composited together.

[0017] Another purpose of the present invention is to induce the composite vacancy-rich O v -CoCuM1-LDH positive electrode material (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and negative electrode material (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-) served as the positive and negative electrodes of the hybrid supercapacitor, respectively.

[0018] Specifically, the prepared (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF electrode material as the positive electrode, (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF electrode material was used as the negative electrode, with 6 mol L -1 The electrochemical performance tests such as cyclic voltammetry (CV) and constant current charge-discharge (GCD) were carried out in three-electrode and two-electrode systems, and the corresponding energy density and power density were calculated to evaluate the prepared (+) (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF / / (Co, Cu, Fe)9S8@O v-CoCuFe-LDH / CF(-) positive and negative electrode materials and the electrochemical performance of hybrid supercapacitors (HSCs). The cyclic voltammetry (CV) test was performed in the voltage range of 0-0.5 V for the positive electrode and -1.0-0.2 V for the negative electrode, with scan rates of 5, 10, 20, 50, and 100 mV s -1 The voltage range of the constant current charge and discharge test was 0~0.5 V, the negative electrode was -0.9~-0.2 V, and the current density was 1, 2, 3, 5, 8 and 10 A g -1 .

[0019] The (Co, Cu, M1)9S8(M1=Ni, Fe)@O prepared by the present invention v -CoCuM1-LDH / CF positive and negative electrode materials were structurally analyzed and their performances were analyzed using field emission scanning electron microscopy (FESEM), energy dispersive spectrometer (EDS), CHI-760E electrochemical workstation and other instruments to evaluate their electrochemical activity.

[0020] LDH has a unique two-dimensional structure with a high specific surface area, adjustable functionalized surface ends, good conductivity and high electrochemical activity. In particular, when combined with highly electronegative sulfur, it forms a stable hierarchical structure of highly active nanoparticles cross-linked with vacancy-rich nanosheets, which can greatly enhance the electrochemical performance of the material.

[0021] The present invention constructs a porous vacancy-rich composite electrode (Co, Cu, M1)9S8(M1=Ni, Fe)@O with a high specific surface integral hierarchical structure on the surface of copper foam (CF) through the synthesis steps of room temperature in-situ oxidation self-assembly-modified Lewis acid solvent heat exchange / etching-solvent heat restricted sulfur composite. v -CoCuM1-LDH / CF. The material utilizes the in-situ growth of (Co, Cu, M1)9S8 (M1=Ni,Fe) nanoparticles to enhance interfacial charge transfer, and high-temperature sulfurization during the synthesis process creates oxygen vacancies (O v ) synergistically broadens the conductive network with doped sulfur and alleviates volume deformation through interlayer confinement effect. Experiments show that the electrode material exhibits ultra-high specific capacitance (positive electrode> 2600 F g -1 , negative electrode>2400 F g -1 ), HSC high energy density (>100 Wh kg -1 ) long cycle life (>10,000 times), which is significantly better than a single-component system, providing an ideal electrode solution for the new generation of high-energy-density and high-stability HSC devices.

[0022] The reactants and reagents used in the present invention are all commercially available, including foamed copper, an oxidant (ammonium persulfate, (NH4)2S2O8), an alkali source (sodium hydroxide, NaOH), a cobalt salt (Co(NO3)2·6H2O), a nickel salt (Ni(NO3)2·6H2O), an iron salt (Fe(NO3)3·9H2O), 2-methylimidazole (C4H6N2), and thioacetamide (TAA, C2H5NS).

[0023] Beneficial effects

[0024] The present invention synthesizes (Co, Cu, M1)9S8(M1=Ni, Fe)@O through four steps: room temperature in-situ oxidation self-assembly, improved Lewis acid solvent heat exchange / etching (two steps), and solvent heat restricted sulfur composite method. v -CoCuM1-LDH / CF composite positive and negative electrode materials. CF and Cu(OH)2-derived nanosheets cross-linked hollow nanocolumn hierarchical structure provides a stable substrate, increasing the conductivity and specific surface area of the material. At the same time, (Co, Cu, M1)9S8 (M1=Ni, Fe) nanoparticles and O v The self-supporting material avoids the need for adhesives when used as positive / negative electrode materials in hybrid supercapacitors, reduces the material's impedance, and significantly improves its electrochemical performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 (Co, Cu, M1)9S8(M1=Ni, Fe)@O prepared in Example 1 v -SEM images (a) and elemental mapping (b) of the CoCu M1-LDH / CF positive and negative electrode materials;

[0026] Figure 2 (Co, Cu, M1)9S8(M1=Ni, Fe)@O prepared in Example 1 v -GCD curves of CoCu M1-LDH / CF positive and negative electrode materials;

[0027] Figure 3 Hybrid supercapacitor assembled with positive and negative electrode materials prepared in Example 1 (+) (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF / / (Co, Cu, Fe)9S8@O v -Energy density-power density diagram of CoCuFe-LDH / CF(-);

[0028] Figure 4 The hybrid supercapacitor prepared in Example 1 (+) (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF / / (Co, Cu, Fe)9S8@O v Cycling stability diagram of -CoCuFe-LDH / CF(-). DETAILED DESCRIPTION

[0029] Below in conjunction with embodiment, the present invention is described in detail so that those skilled in the art can better understand the present invention, but the present invention is not limited to following examples. Unless otherwise limited, the terms used herein (comprising scientific and technological terms) should be interpreted as having the same meaning as commonly understood by those skilled in the art to which the present invention belongs. It will also be understood that the terms used herein should be interpreted as having a meaning consistent with their meaning in the content of this specification and the related art, and should not be interpreted in an idealized or excessive form, unless specifically so defined herein.

[0030] Example 1

[0031] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0032] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 20 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0033] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0034] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0035] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0036] (Co, Cu, M1)9S8(M1=Ni, Fe)@O v -Characterization and analysis of CoCu M1-LDH / CF positive and negative electrode materials

[0037] like Figure 1 As shown in the figure, it can be seen that in the microscopic state, (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles are interspersed in the cross-linked layered material O v -CoCuNi-LDH, a cross-linked hierarchical composite structure, especially the micron-sized ZIFs polyhedron structure appears on the negative electrode, which has an ultra-high specific surface area and stability. Element mapping can better see the uniform dispersion distribution of elements, indicating the successful synthesis of the electrode material.

[0038] like Figure 2 As shown in the figure, we can see that the positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF (+) and (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-)GCD curve, it can be calculated that the positive and negative electrode materials have a current density of 1 A g -1 2685 F g -1 , 2467 F g -1high specific capacity.

[0039] like Figure 3 As shown, the hybrid supercapacitor (+) (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF / / (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-)) is used in the application of two-electrode system. From the energy density-power density diagram, it can be seen that the assembled hybrid supercapacitor has good power density and energy density. When its power density is 800 W kg -1 The maximum energy density that can be achieved is 115.4 Wh kg -1 .

[0040] like Figure 4 As shown, the hybrid supercapacitor (+) (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF / / (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-)) underwent cycle stability test and showed a capacity retention rate of 114% after 10,000 cycles, demonstrating good cycle performance.

[0041] Example 2

[0042] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0043] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 10 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0044] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0045] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0046] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0047] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 89.2%, showing good cycle performance.

[0048] Example 3

[0049] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0050] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 30 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0051] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0052] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0053] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0054] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 95.1%, showing good cycle performance.

[0055] Example 4

[0056] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0057] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 20 mL of deionized water. Stir for 10 minutes. 2) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0058] Step 2: Weigh 150 mg of cobalt nitrate, 100 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0059] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0060] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0061] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 93.3%, showing good cycle performance.

[0062] Example 5

[0063] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0064] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 20 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0065] Step 2: Weigh 150 mg of cobalt nitrate, 300 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0066] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0067] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0068] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 87.8%, showing good cycle performance.

[0069] Example 6

[0070] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v- A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0071] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 10 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0072] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0073] Step 3: Weigh 100 mg of cobalt nitrate, 50 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0074] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0075] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 94.1%, showing good cycle performance.

[0076] Example 7

[0077] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0078] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 10 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0079] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0080] Step 3: Weigh 100 mg of cobalt nitrate, 150 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0081] Step 4: Weigh 1 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and (Co, Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0082] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 83.5%, showing good cycle performance.

[0083] Example 8

[0084] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0085] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 10 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0086] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0087] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0088] Step 4: Weigh 0.5 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich O v -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v-CoCuNi-LDH / CF (+) and (Co,Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0089] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 91.3%, showing good cycle performance.

[0090] Example 9

[0091] A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, comprises the following steps:

[0092] Step 1: Weigh 0.45 g of ammonium persulfate and 2 g of sodium hydroxide and dissolve them in 10 mL of deionized water. Stir for 10 minutes. 2 ) was placed in the mixed solution and subjected to in-situ oxidation self-assembly reaction at room temperature for 20 minutes. After washing with deionized water and ethanol, it was dried at 60 °C to obtain a nanopillar array electrode Cu(OH)2 / CF;

[0093] Step 2: Weigh 150 mg of cobalt nitrate, 150 mg of nickel nitrate, and 300 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuNi-LDH / CF electrode.

[0094] Step 3: Weigh 100 mg of cobalt nitrate, 100 mg of ferric nitrate, and 200 mg of 2-MI and dissolve them in 20 mL of methanol. Stir thoroughly for 5 min, immerse the prepared Cu(OH)2 / CF electrode in the above solution, and react at 120 °C for 6 h. After the reactor cools to room temperature, remove the sample, wash it several times with deionized water and anhydrous ethanol, and dry it at 60 °C to obtain a CoCuFe-LDH / CF electrode.

[0095] Step 4: Weigh 1.5 mg of TAA and dissolve it in 20 mL of ethanol. Immerse the prepared CoCuM1-LDH (M1 = Ni, Fe) / CF electrode in the above solution and react at 120 °C for 2 h. After the reactor cools to room temperature, take out the sample, wash it with deionized water and anhydrous ethanol several times, and dry it at 60 °C to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles composited with vacancy-rich Ov -CoCuM1-LDH positive and negative electrode materials (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF (+) and (Co,Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-).

[0096] The prepared positive and negative electrode materials were used as positive and negative electrodes of hybrid supercapacitors for cycle stability testing. The results showed that after 10,000 cycles, the capacity retention rate was 90.4%, showing good cycle performance.

[0097] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the description of the present invention, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A (Co, Cu, M1)9S8 nanoparticle-induced composite vacancy-rich O v - A method for preparing a CoCuM1-LDH electrode material, wherein M1 = Ni, Fe, characterized in that: The following steps are involved: A. Immerse the copper foam CF in a deionized water solution containing an oxidant and an alkali source for in-situ oxidation self-assembly reaction for 1-30 min, then wash and dry to obtain a nanorod array electrode Cu(OH)2 / CF; B. Immerse the nanopillar array electrode Cu(OH)2 / CF in a methanol solution containing a cobalt source, a nickel source, and a 2-MI solution, transfer it into a reactor and react at 100-140°C for 4-8 hours. After cooling naturally to room temperature, take it out and wash it with deionized water and anhydrous ethanol several times. Dry it at 60°C to obtain a columnar hierarchical structure CoCuNi-LDH / CF cross-linked with 2-MI intercalated and substituted layered double hydroxide nanosheets. C. Immerse the nanopillar array electrode Cu(OH)2 / CF in a methanol solution containing a cobalt source, an iron source, and a 2-MI solution, move it into a reactor, and react at 100-140°C for 4-8 h, preferably at 120°C for 6 h. After cooling naturally to room temperature, take it out, wash it with deionized water and anhydrous ethanol several times, and dry it at 60°C to obtain a columnar hierarchical structure CoCuFe-LDH / CF with 2-MI intercalated and substituted layered double hydroxide nanosheets cross-linked with ZIFs polyhedrons; D. The cross-linked columnar hierarchical structure CoCuM1-LDH (M1 = Ni, Fe) / CF prepared in steps B and C was mixed with an ethanol solution containing a sulfur source and reacted in an autoclave at 100-140°C for 1-3 hours, preferably at 120°C for 2 hours. The obtained product was washed with deionized water and ethanol, and dried to obtain (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles induced composite vacancy-rich O v -CoCuM1-LDH positive electrode material (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and negative electrode material (Co,Cu,Fe)9S8@O v -CoCuFe-LDH / CF(-).

2. (Co, Cu, M1)9S8 nanoparticles induced composite vacancy-rich O according to claim 1 v -The preparation method of CoCuM1-LDH electrode material is characterized by: In step A, the foam copper CF is immersed in a deionized water solution added with an oxidant and an alkali source to perform an in-situ oxidation self-assembly reaction for 20 minutes, and then washed and dried to obtain the foam copper CF.

3. (Co, Cu, M1)9S8 nanoparticles induced composite vacancy-rich O according to claim 1 v -The preparation method of CoCuM1-LDH electrode material is characterized by: In step A, the material ratio of copper foam CF, oxidant, alkali source and deionized water is 1~3cm 2 : 0.3~0.6g: 1~3g: 10~30mL, preferably 2cm 2 : 0.45g: 2g: 20mL, wherein the oxidant is ammonium persulfate or sodium persulfate, preferably ammonium persulfate; the alkali source is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.

4. (Co, Cu, M1)9S8 nanoparticles induced composite vacancy-rich O according to claim 1 v -The preparation method of CoCuM1-LDH electrode material is characterized by: In step B, the Cu(OH)2 / CF nanorod array electrode is immersed in a methanol solution containing a cobalt source, a nickel source, and a 2-MI solution, moved into a reactor, reacted at 120°C for 6 hours, naturally cooled to room temperature, taken out, washed several times with deionized water and anhydrous ethanol, and dried at 60°C.

5. (Co, Cu, M1)9S8 nanoparticles induced composite vacancy-rich O according to claim 1 v -The preparation method of CoCuM1-LDH electrode material is characterized by: In step B, the material ratio of cobalt source, nickel source, 2-MI and methanol is 100~300 mg:100~300 mg:300~500 mg:10~30 mL, preferably 150 mg:150 mg:300 mg:20 mL; wherein the cobalt source is Co(NO3)2 or CoCl2, preferably Co(NO3)2, and the nickel source is Ni(NO3)2 or NiCl2, preferably Ni(NO3)2.

6. (Co, Cu, M1)9S8 nanoparticles induced composite vacancy-rich O according to claim 1 v -The preparation method of CoCuM1-LDH electrode material is characterized by: In step C, the material ratio of cobalt source, iron source, 2-MI and methanol is 50~150mg:50~150mg:100~300mg:10~30mL, preferably 100mg:100mg:200mg:20mL; wherein the cobalt source is Co(NO3)2 or CoCl2, preferably Co(NO3)2, and the iron source is Fe(NO3)2 or FeCl2, preferably Fe(NO3)2.

7. (Co, Cu, M1)9S8 nanoparticles induced composite vacancy-rich O according to claim 1 v -The preparation method of CoCuM1-LDH electrode material is characterized by: In step D, the material ratio of the nanosheet cross-linked columnar hierarchical structure CoCuM1-LDH (M1 = Ni, Fe) / CF, sulfur source, and ethanol solution is 1~3cm 2 : 0.5~1.5mg: 10-30mL, preferably 2cm 2 : 1.0 mg: 20 mL; wherein the sulfur source is thioacetamide (TAA) or sodium sulfide (Na2S), preferably TAA.

8. Positive electrode material (Co, Cu, Ni)9S8@O prepared by the method according to any one of claims 1 to 7 v -CoCuNi-LDH / CF(+) and negative electrode material (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-).

9. The positive electrode material (Co, Cu, Ni)9S8@O according to claim 6 v -CoCuNi-LDH / CF(+) and negative electrode material (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-), characterized by: Its microstructure is (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles and vacancy-rich O v -CoCuM1-LDH nanosheets are cross-linked to form hollow nanocolumns composited together.

10. Use of the electrode material according to claim 8 or 9, characterized in that: The prepared (Co, Cu, M1)9S8 (M1 = Ni, Fe) nanoparticles induce the composite vacancy-rich O v -CoCuM1-LDH positive electrode material (Co, Cu, Ni)9S8@O v -CoCuNi-LDH / CF(+) and negative electrode material (Co, Cu, Fe)9S8@O v -CoCuFe-LDH / CF(-) served as the positive and negative electrodes of the hybrid supercapacitor, respectively.

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