阅读说明：本技术 一种v3o5纳米电极材料的制备方法 (V-shaped groove3O5Preparation method of nano electrode material ) 是由 黄剑锋 王羽偲嘉 李嘉胤 曹丽云 罗晓敏 胡云飞 王芳敏 于 2021-01-18 设计创作，主要内容包括：本发明公开了一种V-3O-5纳米电极材料的制备方法。通过溶剂热-煅烧法两部分得到,将钒源与硫源混合进行溶剂热反应,然后将钒硫混合物在管式炉中煅烧得到最终产品。本发明提供的V-3O-5结构为100nm左右的纳米颗粒,结构均匀,分布均一,稳定性好。本发明合成V-3O-5将粒径尺寸缩小在纳米尺寸范围内,具有良好的电化学性能。(The invention discloses a V 3 O 5 A preparation method of a nano electrode material. The vanadium-sulfur composite material is obtained by a solvothermal-calcination method, a vanadium source and a sulfur source are mixed for solvothermal reaction, and then the vanadium-sulfur mixture is calcined in a tubular furnace to obtain a final product. V provided by the invention 3 O 5 The structure is about 100nm of nano particles, the structure is uniform, the distribution is uniform, and the stability is good. Synthesis of V according to the invention 3 O 5 The particle size is reduced to be in a nanometer size range, and the electrochemical performance is good.)

1. V-shaped groove₃O₅The preparation method of the nano electrode material is characterized by comprising the following steps of:

the method comprises the following steps: firstly, mixing a vanadium source and a sulfur source according to a molar ratio of 1: 3-5.85, adding the mixture into absolute ethyl alcohol, uniformly stirring at room temperature, carrying out solvothermal reaction on the mixed solution, collecting a product, washing the product, and freeze-drying the product to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 450-550 ℃ at a heating rate of 5-10 ℃/min in a tube furnace inert atmosphere, calcining to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

2. V according to claim 1₃O₅The preparation method of the nano electrode material is characterized by comprising the following steps: the vanadium source is one or a mixture of sodium metavanadate, sodium vanadate and vanadium acetylacetonate.

3. V according to claim 1₃O₅The preparation method of the nano electrode material is characterized by comprising the following steps: the sulfur source is one or a mixture of thioacetamide, thiourea and cysteine.

4. V according to claim 1₃O₅The preparation method of the nano electrode material is characterized by comprising the following steps: the stirring time is 0.5-2 h.

5. V according to claim 1₃O₅The preparation method of the nano electrode material is characterized by comprising the following steps: the solvothermal reaction temperature is 160-180 ℃, and the reaction time is 18-24 h.

6. V according to claim 1₃O₅The preparation method of the nano electrode material is characterized by comprising the following steps: the calcination time is 2-4 hours.

Technical Field

The invention relates to the field of battery electrode materials, in particular to a V₃O₅A preparation method of a nano electrode material.

Background

With the shortage of chemical energy and the pollution to the environment, new energy which is sustainable and pollution-free is receiving more and more attention. Lithium ion batteries have been attracting attention as one of the most advanced rechargeable batteries due to their advantages of low cost, environmental protection, high energy density, and the like over the last several decades. The electrochemical properties of lithium ion batteries, including cyclability, rate capability, energy density, etc., are significantly affected by the anode material selected. Carbon remains the dominant product of commercial lithium ion batteries today since the first commercialization of carbonaceous anodes. The graphite carbon having a layered structure can promote movement of lithium ions into and out of the lattice space, and has excellent cyclability. However, the theoretical capacity of graphite is low, and cannot meet the requirement of future social development, and the development of more excellent negative electrode materials is imminent (Jang B Z, Liu C, Neff D, et al]Nano Letters,11(2011): 3785-. The vanadium oxide electrode material is a candidate of excellent lithium ion battery cathode materials due to the advantages of high theoretical capacity, abundant reserves and the like. V₃O₅The lithium ion battery cathode material is of great interest as a new lithium ion battery cathode material due to excellent cycling stability and rate capability (Chen D, Tan H, Rui X, et al₃O₅:A new intercalation-type anode for lithium-ion battery[J].InfoMat,2019,1.)

Disclosure of Invention

The invention aims to provide a novel V with simple process, low raw material cost, low cost and high yield₃O₅A preparation method of a nano electrode material.

In order to achieve the purpose, the invention adopts the technical scheme that:

the method comprises the following steps: firstly, mixing a vanadium source and a sulfur source according to a molar ratio of 1: 3-5.85, adding the mixture into absolute ethyl alcohol, uniformly stirring at room temperature, carrying out solvothermal reaction on the mixed solution, collecting a product, washing the product, and freeze-drying the product to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 450-550 ℃ at a heating rate of 5-10 ℃/min in a tube furnace inert atmosphere to calcine the vanadium-sulfur composite material to obtain black powder, and grinding the black powder to obtain V₃O₅A nanoelectrode material.

The vanadium source is one or a mixture of sodium metavanadate, sodium vanadate and vanadium acetylacetonate.

The sulfur source is one or a mixture of thioacetamide, thiourea and cysteine.

The stirring time is 0.5-2 h.

The solvothermal reaction temperature is 160-180 ℃, and the reaction time is 18-24 h.

The calcination time is 2-4 hours.

Compared with the prior art, the invention has the following beneficial effects:

1) the invention provides a new V₃O₅A preparation method. Preparation of V by solvothermal-calcination two-step method₃O₅The nano electrode material has the advantages of simple process, low cost of raw materials, low cost, high yield and the like, and is suitable for large-scale production.

2) V prepared by the invention₃O₅The purity and the crystallinity of the electrode material are high.

3) V prepared by the invention₃O₅The electrode material has small size, is nano-scale particles and has uniform structure.

4) V prepared by the invention₃O₅The lithium ion battery anode material is a novel battery anode material and still keeps good stability under high current density.

Drawings

FIG. 1 is V prepared in example 4₃O₅The XRD diffractogram of (1), wherein the abscissa is the angle 2 θ and the ordinate is the intensity.

FIG. 2 is V prepared in example 4₃O₅SEM image of (d).

FIG. 3 is V prepared in example 4₃O₅The abscissa is the number of cycles and the ordinate is the number of cyclesThe coordinates are capacity (mAh/g).

Detailed Description

Example 1:

the method comprises the following steps: firstly, mixing sodium metavanadate and thioacetamide according to a molar ratio of 1: 3, adding the mixture into absolute ethyl alcohol, stirring the mixture for 0.5 hour at room temperature, uniformly stirring the mixture, carrying out solvothermal reaction on the mixed solution for 18 hours at 160 ℃, collecting a product, washing the product, and carrying out freeze drying to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 450 ℃ at the heating rate of 5 ℃/min in the inert atmosphere of a tubular furnace, calcining for 2 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

Example 2:

the method comprises the following steps: firstly, mixing sodium vanadate and thiourea according to a molar ratio of 1: 3.5 dissolving in absolute ethyl alcohol, stirring for 1h at room temperature, carrying out solvothermal reaction on the mixed solution for 18h at 180 ℃, collecting a product, washing, and freeze-drying to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 500 ℃ at the heating rate of 8 ℃/min in the inert atmosphere of a tube furnace, calcining for 3 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

Example 3:

the method comprises the following steps: firstly, mixing sodium metavanadate and thioacetamide according to a molar ratio of 1: 4, dissolving the mixed solution in absolute ethyl alcohol, stirring the mixed solution for 1 hour at room temperature, carrying out solvothermal reaction on the mixed solution for 20 hours at 180 ℃, collecting a product, washing the product, and freeze-drying the product to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 500 ℃ at a heating rate of 10 ℃/min in a tube furnace inert atmosphere, calcining for 4 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

Example 4:

the method comprises the following steps: firstly, mixing sodium metavanadate and thioacetamide according to a molar ratio of 1: 5.85 dissolving in absolute ethyl alcohol, stirring for 2h at room temperature, carrying out solvothermal reaction on the mixed solution for 24h at 180 ℃, collecting a product, washing, and freeze-drying to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 550 ℃ at the heating rate of 5 ℃/min in the inert atmosphere of a tube furnace, calcining for 2 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

As can be seen from FIG. 1, the diffraction peaks all point to JCPDS72-0524 PDF card, proving that V is synthesized₃O₅。

The resultant V can be seen in FIG. 2₃O₅Is about 100nm of nano-particles.

FIG. 3 is V₃O₅The multiplying power performance graphs of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 5A/g and 0.1A/g can be seen from FIG. 3, and V is shown₃O₅The reversibility of the electrode material is good, and the capacity of 180mAh/g can still be kept when the current returns to the current density of 0.1A/g.

Example 5:

the method comprises the following steps: firstly, mixing sodium vanadate and cysteine according to a molar ratio of 1: 5, adding the mixed solution into absolute ethyl alcohol, stirring the mixed solution for 1.5 hours at room temperature, carrying out solvothermal reaction on the mixed solution for 20 hours at 160 ℃, collecting a product, washing the product, and carrying out freeze drying to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 500 ℃ at the heating rate of 8 ℃/min in the inert atmosphere of a tube furnace, calcining for 3 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

Example 6:

the method comprises the following steps: firstly, mixing vanadium acetylacetonate and thioacetamide according to a molar ratio of 1: 4.5 dissolving in absolute ethyl alcohol, stirring for 2h at room temperature, carrying out solvothermal reaction on the mixed solution for 24h at 160 ℃, collecting a product, washing, and freeze-drying to obtain the vanadium-sulfur composite material;

step two: calcining the vanadium-sulfur composite material in a tube furnace inert atmosphere at the temperature rise rate of 10 ℃/min from the room temperature blast to 500 ℃ for 2.5 hours to obtain black powder, and grinding the black powder to obtain V₃O₅A nanoelectrode material.

Example 7:

the method comprises the following steps: firstly, mixing sodium metavanadate, sodium vanadate, thioacetamide and thiourea according to a molar ratio of 1: 5.5 dissolving in absolute ethyl alcohol, stirring for 1h at room temperature, carrying out solvothermal reaction on the mixed solution for 22h at 180 ℃, collecting a product, washing, and freeze-drying to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 500 ℃ at the heating rate of 7 ℃/min in the inert atmosphere of a tube furnace, calcining for 3 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.

Example 8:

the method comprises the following steps: firstly, mixing sodium vanadate, vanadium acetylacetonate, thioacetamide and cysteine according to a molar ratio of 1: 5.85 dissolving in absolute ethyl alcohol, stirring for 2h at room temperature, carrying out solvothermal reaction on the mixed solution for 24h at 180 ℃, collecting a product, washing, and freeze-drying to obtain the vanadium-sulfur composite material;

step two: heating the vanadium-sulfur composite material from room temperature to 550 ℃ at a heating rate of 10 ℃/min in a tube furnace inert atmosphere, calcining for 2 hours to obtain black powder, and grinding to obtain V₃O₅A nanoelectrode material.