Method for preparing nano needle-shaped basic cupric carbonate-nickel supercapacitor electrode material at ultra-fast speed

Abstract

The invention relates to a method for preparing a nano needle-shaped basic cupric carbonate-nickel supercapacitor electrode material at an ultra-fast speed. A water-soluble copper compound and urea are used as basic raw materials, and a water-soluble nickel compound is used as an accelerant; the preparation method comprises the following steps: firstly, preparing a solution containing 0.01 to 0.50 mol / L of Cu < 2 + >, 0.01 to 0.50 mol / L of Ni < 2 + > and 0.2 to 0.5 mol / L of urea at the same time; then transferring the solution into a reaction kettle; and keeping the temperature of the reaction kettle at 105-135 DEG C for 30-60 minutes to obtain the single-crystal needle-shaped basic copper carbonate-nickel with the specific capacitance of more than 2300F / g. The method has the advantages that the hydrothermal reaction speed is high, the period is short and is not longer than 1 h, and the prepared nanometer needle-shaped basic copper carbonate-nickel has ultrahigh 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 between traditional capacitors and rechargeable batteries. They have the advantages of fast charging and discharging of capacitors and the energy storage characteristics of batteries. Supercapacitors are new components that store energy through the interface formed between electrodes and electrolytes. Therefore, the larger the specific surface area of ​​the electrode and the better the permeability of the electrolyte solution, the more conducive it is to improving the performance of the supercapacitor. Among the many morphologies, the urchin-shaped / hedgehog-shaped structure is undoubtedly the most able to meet this requirement.

[0003] Basic carbonates have good theoretical specific capacity as supercapacitor electrode materials. At the same time, it is well known that the hydrothermal method can be combined with urea as a surfactant to prepare sea urchin-shaped basic carbonates (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 the 2+ A certain concentration of Ni is added to the aqueous solution of urea 2+ When the reaction time is reduced significantly (≤1h), the urchin-like basic copper-nickel carbonate with a nano-needle structure can be 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 microscopic morphology of the product is not 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, produces more micromicelles, and 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] In view of the shortcoming of the long hydrothermal reaction cycle in the prior art, the present invention proposes a method for ultra-fast preparation of nano needle-shaped basic copper carbonate-nickel supercapacitor electrode material. 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, a Cu-containing solution of 0.01-0.50 mol / L is prepared. 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 reaction kettle; the reaction kettle is kept at 105-135° C. for 30-60 min to obtain 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, which is no more than 1 hour, and the prepared nano needle-shaped basic copper-nickel carbonate has an ultra-high specific capacitance. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0013] Figure 2 This is the SEM image (low magnification - 50000 times) of the nano needle-shaped basic copper-nickel carbonate prepared in Example 1.

[0014] Figure 3 This is the SEM image (low magnification - 200000 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 implementation modes.

[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 Cu 2+, 0.1 mol / L Ni 2+ and 0.5 mol / L urea solution; then the solution was transferred into a reactor; the reactor was kept at 120°C for 30 min to obtain needle-shaped basic copper-nickel carbonate (atomic ratio 1:1, Figure 1 , Figure 2-3 Their XRD and SEM images are shown 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, first prepare a solution containing 0.1 mol / 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 2475 F / 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, first prepare a solution containing 0.01 mol / 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 2380 F / 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, a Cu(NO3)2 solution containing 0.05 mol / L was prepared. 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 2315 F / 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, first prepare a CuSO4 / CuCl2 solution containing 0.5 mol / L. 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 2387 F / g.

Claims

1. A method for ultra-fast preparation of nano-needle-shaped basic copper carbonate-nickel supercapacitor electrode material, characterized in that: Using water-soluble copper compounds and urea as the basic raw materials and water-soluble nickel compounds as the accelerator; firstly, a Cu-containing solution of 0.01-0.50 mol / L is prepared. 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 reaction kettle; the reaction kettle is kept at 105-135° C. for 30-60 min 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-needle-shaped basic copper carbonate-nickel 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-needle-shaped basic copper carbonate-nickel 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-needle-shaped basic copper carbonate-nickel 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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