A method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material

Abstract

The present invention relates to a method for ultra-fast preparation of nano needle-shaped basic copper-nickel carbonate supercapacitor electrode materials. Water-soluble copper compounds and urea are used as basic raw materials, and water-soluble nickel compounds are used as promoters. First, a Cu-containing 0.01-0.50 mol / L 2+ , 0.01~0.50mol / L Ni 2+ A solution containing 0.2-0.5 mol / L urea is prepared; the solution is then transferred to a reactor. The reactor is kept at 105-135°C for 30-60 minutes to produce single-crystal needle-shaped basic copper-nickel carbonate with a specific capacitance exceeding 2300 F / g. This method features a fast hydrothermal reaction and a short cycle time of less than 1 hour. The resulting nano-needle-shaped basic copper-nickel carbonate exhibits ultra-high specific capacitance.

Description

Technical Field

[0001] The invention provides a method for ultra-fast preparation of nano needle-shaped basic copper carbonate-nickel supercapacitor electrode materials, belonging to the field of supercapacitor electrode materials. Background Art

[0002] Supercapacitors are a new type of energy storage device, a cross between traditional capacitors and rechargeable batteries. They combine the rapid charge and discharge capabilities of capacitors with the energy storage characteristics of batteries. Supercapacitors are novel components that store energy through the interface formed between electrodes and electrolytes. Therefore, a larger electrode surface area and greater electrolyte permeability contribute to improved supercapacitor performance. Among various morphologies, sea urchin / hedgehog-like structures undoubtedly best meet these requirements.

[0003] Basic carbonate has a good theoretical specific capacity as a supercapacitor electrode material. At the same time, as is well known, by combining the hydrothermal method with urea as a surfactant, sea urchin-shaped basic carbonates can be prepared (CN 115261913 A, CN 109781795B, etc.). However, this method basically has the problems of long preparation cycle and low production efficiency. In particular, as basic copper carbonate (CN 104760987 A) and basic nickel carbonate (Liang Yuanyong. Hydrothermal preparation and adsorption properties of special morphology basic nickel carbonate and nickel oxide [D]. Northeastern University, 2021.) with higher theoretical specific capacity, the problem in this regard is particularly prominent, and the preparation hydrothermal reaction cycle is ≥8h.

[0004] It was accidentally discovered in the experiment that only Cu 2+ A certain concentration of Ni is added to the aqueous solution of urea 2+ When the reaction time is reduced significantly (≤1h), the obtained copper-nickel carbonate with a sea urchin-like structure and a nano-needle structure is obtained. When used as a supercapacitor electrode, the product has an ultra-high specific capacity. However, when an alcohol solution is added, the reaction time is greatly extended, and the microstructure of the obtained product is not sea urchin-like. Principle: Ni 2+ After adding Cu 2+ A synergistic effect is formed, which promotes the hydrolysis of urea in the solution, generates amino and hydroxyl ions more quickly, and produces more micelles, which greatly shortens the cycle of the hydrothermal reaction; and the addition of alcohol solution inhibits the hydrolysis reaction of urea. Summary of the Invention

[0005] To address the shortcomings of the prior art in terms of long hydrothermal reaction cycles, the present invention proposes an ultra-fast method for preparing nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode materials. The present invention is achieved through the following technical solutions.

[0006] A method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material, the specific steps of which are as follows:

[0007] Using water-soluble copper compounds and urea as the basic raw materials and water-soluble nickel compounds as the accelerator; firstly, prepare a solution containing 0.01-0.50 mol / L of Cu 2+ , 0.01~0.50mol / L Ni 2+ and a solution of 0.2-0.5 mol / L urea; then the solution is transferred into a reactor; the reactor is kept at 105-135° C. for 30-60 minutes to obtain a nano needle-shaped basic copper-nickel carbonate with a specific capacitance of more than 2300 F / g.

[0008] The water-soluble copper compound is one or more of copper chloride, copper sulfate and copper nitrate.

[0009] The water-soluble nickel compound is one or more of nickel chloride, nickel sulfate and nickel nitrate.

[0010] The atomic ratio of copper to nickel in the basic copper-nickel carbonate is 1:10 to 10:1.

[0011] The beneficial effects of the present invention are as follows: the hydrothermal reaction speed is fast and the cycle is short, no more than 1 hour, and the prepared nano needle-shaped basic copper-nickel carbonate has ultra-high specific capacitance. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 1 is the XRD pattern of the nano needle-shaped basic copper-nickel carbonate prepared in Example 1.

[0013] Figure 2 This is an SEM image (low magnification to 50,000 times) of the nano needle-shaped basic copper-nickel carbonate prepared in Example 1.

[0014] Figure 3 This is an SEM image (low magnification - 200,000 times) of the nano needle-shaped basic copper-nickel carbonate prepared in Example 1. DETAILED DESCRIPTION

[0015] The present invention will be further described below in conjunction with specific embodiments.

[0016] Example 1

[0017] The method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material comprises the following steps:

[0018] Using water-soluble CuCl2.2H2O and urea as the basic raw materials and water-soluble NiCl2.6H2O as the promoter; firstly prepare a solution containing 0.1mol / L Cu 2+, 0.1 mol / L Ni 2+ and 0.5 mol / L urea solution; then the solution was transferred into the reactor; the reactor was kept at 120 ° C for 30 min to obtain needle-shaped basic copper carbonate-nickel (atomic ratio 1:1, Figure 1 、 Figure 2-3 XRD and SEM images respectively).

[0019] Example 2

[0020] The method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material comprises the following steps:

[0021] Using water-soluble Cu(NO3)2 and urea as the basic raw materials and water-soluble NiSO4 as the promoter; firstly, prepare a solution containing 0.1mol / L Cu 2+ , 0.01 mol / L Ni 2+ and 0.4 mol / L urea solution; then the solution is transferred into a reactor; the reactor is kept at 110°C for 55 minutes to obtain needle-shaped basic copper-nickel carbonate (atomic ratio 10:1) with a specific capacitance of 2475F / g.

[0022] Example 3

[0023] The method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material comprises the following steps:

[0024] Using water-soluble CuSO4 and urea as the basic raw materials and water-soluble Ni(NO3)2 as the promoter; firstly, prepare a solution containing 0.01mol / L Cu 2+ , 0.1 mol / L Ni 2+ and 0.2 mol / L urea solution; then the solution is transferred into a reactor; the reactor is kept at 105°C for 60 minutes to obtain needle-shaped basic copper-nickel carbonate (atomic ratio 1:10) with a specific capacitance of 2380F / g.

[0025] Example 4

[0026] The method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material comprises the following steps:

[0027] Using water-soluble Cu(NO3)2 and urea as the basic raw materials and water-soluble NiSO4 / Ni(NO3)2 as the promoter; firstly, prepare a solution containing 0.05mol / L Cu 2+ , 0.05 mol / L Ni 2+and 0.4 mol / L urea solution; then the solution is transferred into a reactor; the reactor is kept at 135°C for 35 minutes to obtain needle-shaped basic copper-nickel carbonate (atomic ratio 1:1) with a specific capacitance of 2315F / g.

[0028] Example 5

[0029] The method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material comprises the following steps:

[0030] Using water-soluble CuSO4 / CuCl2 and urea as the basic raw materials and water-soluble Ni(NO3)2 as the promoter; firstly, prepare a solution containing 0.5mol / L Cu 2+ , 0.1 mol / L Ni 2+ and 0.5 mol / L urea solution; then the solution is transferred into a reactor; the reactor is kept at 130°C for 40 minutes to obtain needle-shaped basic copper-nickel carbonate (atomic ratio 5:1) with a specific capacitance of 2387F / g.

Claims

1. A method for ultra-fast preparation of nano-acicular basic copper-nickel carbonate supercapacitor electrode material, characterized by: Using water-soluble copper compounds and urea as the basic raw materials and water-soluble nickel compounds as the promoter; firstly, prepare a solution containing 0.01-0.50 mol / L of Cu 2+ , 0.01~0.50mol / L Ni 2+ and a solution of 0.2-0.5 mol / L urea; then the solution is transferred into a reactor; the reactor is kept at 105-135° C. for 30-60 minutes to obtain a single crystal needle-shaped basic copper-nickel carbonate with a specific capacitance of more than 2300 F / g.

2. The method for ultra-fast preparation of nano-acicular basic copper-nickel carbonate supercapacitor electrode material according to claim 1, characterized in that: The water-soluble copper compound is one or more of copper chloride, copper sulfate and copper nitrate.

3. The method for ultra-fast preparation of nano-acicular basic copper-nickel carbonate supercapacitor electrode material according to claim 1, characterized in that: The water-soluble nickel compound is one or more of nickel chloride, nickel sulfate and nickel nitrate.

4. The method for ultra-fast preparation of nano-acicular basic copper-nickel carbonate supercapacitor electrode material according to claim 1, characterized in that: The atomic ratio of copper to nickel in the basic copper-nickel carbonate is 1:10 to 10:1.

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