阅读说明：本技术 一种铜负载三元纳米带正极材料的制备方法及其产品和应用 (Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof ) 是由 崔大祥 吴晓燕 林琳 王岩岩 徐少洪 金彩虹 于 2020-06-11 设计创作，主要内容包括：本发明提供一种铜负载三元纳米带正极材料的制备方法及其产品和应用,本发明利用水热法与原位还原相结合制备铜负载三元纳米带正极材料。铜能够提高材料的电导率且该结构具有较大的比表面积,能够与电解液充分接触,进而可以提高材料的电化学性能。在1C倍率下首次放电比容量约为174 mAh/g,经过50次循环后放电比容量为138 mAh/g。并且制备方法简单,工艺条件容易实现,能量消耗低,且制备无污染。(The invention provides a preparation method of a copper-loaded ternary nanoribbon cathode material, a product and application thereof. Copper can improve the conductivity of the material, and the structure has a large specific surface area and can be fully contacted with electrolyte, so that the electrochemical performance of the material can be improved. The first discharge specific capacity is about 174 mAh/g under the multiplying power of 1C, and the discharge specific capacity is 138 mAh/g after 50 times of circulation. And the preparation method is simple, the process conditions are easy to realize, the energy consumption is low, and the preparation is pollution-free.)

1. A preparation method of a copper-loaded ternary nanoribbon cathode material is characterized in that the copper-loaded ternary nanoribbon cathode material is prepared by combining a hydrothermal method and in-situ reduction, and comprises the following steps:

(1) dissolving lithium salt, nickel salt, cobalt salt, manganese salt and 1 mL of nitric acid in deionized water to ensure that the molar weight ratio of the lithium salt, the nickel salt, the cobalt salt and the manganese salt is 1: 1-x-y: x: y, and stirring to obtain a uniform and clear precursor solution; adding the mixed solution into 15 mL of sodium hydroxide alkali solution, moving the mixed solution into a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 180-200 ℃ for 1-3 h; centrifuging a product after reaction, washing precipitates obtained after centrifugation for many times by using deionized water and absolute ethyl alcohol, drying, and grinding by using an agate mortar to obtain a ternary nanobelt anode material;

(2) dissolving 0.005-0.01 mol of copper oxide in deionized water, stirring for 10-20 min, and then dropwise adding 5-10 mL of ammonia water to obtain a solution A; dissolving 5-10 g of sodium dodecyl benzene sulfonate in 50mL of deionized water, and stirring until the solution is transparent to obtain a solution B; dropwise adding the solution B into the solution A, and stirring for 5-10 hours after dropwise adding to obtain a solution C; adding the product obtained in the step (1) into the solution C to obtain a solution D; dropwise adding 2-5 mmol of reducing agent into the solution D, continuously stirring for 3-6 h, washing the obtained precipitate with deionized water and ethanol for several times, carrying out suction filtration, and drying to obtain a final product.

2. The method for preparing the copper-supported ternary nanoribbon cathode material as claimed in claim 1, wherein the lithium salt is one or a combination of lithium acetate and lithium nitrate.

3. The method for preparing the copper-supported ternary nanoribbon cathode material as claimed in claim 1, wherein the nickel salt is one or a combination of nickel acetate and nickel nitrate.

4. The method for preparing the copper-supported ternary nanoribbon cathode material according to claim 1, wherein the cobaltate is one or a combination of cobalt acetate and cobalt nitrate.

5. The method for preparing the copper-supported ternary nanoribbon cathode material as claimed in claim 1, wherein the manganate is one of manganese acetate and manganese nitrate or a combination thereof.

6. The method for preparing the copper-supported ternary nanoribbon cathode material as claimed in claim 1, wherein the reducing agent is one or a combination of ascorbic acid and sodium borohydride.

7. A copper-supported ternary nanoribbon cathode material, characterized in that it is prepared according to the method of any one of claims 1 to 6.

8. Use of the copper-supported ternary nanoribbon positive electrode material of claim 7 in a lithium ion battery.

Technical Field

The invention relates to a preparation method of a lithium battery positive electrode material, in particular to a preparation method of a copper-loaded ternary nanobelt positive electrode material, and a product and application thereof.

Background

With the rapid development of smaller, lighter and higher performance electronic and communication devices, there is an increasing demand for the performance of batteries that provide power to these devices, particularly with respect to energy. However, the specific capacities of lithium ion batteries and MH/Ni batteries which are commercialized at present are difficult to be improved continuously. Therefore, the development of batteries with higher specific energy is urgently required. Lithium ion secondary batteries have been widely used as high specific energy chemical power sources in the fields of mobile communication, notebook computers, video cameras, portable instruments and meters, and the like, and have rapidly developed into one of the most important secondary batteries at present. Lithium ion batteries, which are the latest generation of green high-energy storage batteries, have been rapidly developed in the early 90 s of the 20 th century, and are favored because of their advantages of high voltage, high energy density, long cycle life, little environmental pollution, and the like.

The ternary material is the first choice material of the lithium battery due to low price and stable performance. Due to the ternary material LiNi_1-x-yCo_xMn_yO₂（0<x<1, 0<y<1) Has the characteristics superior to lithium iron phosphate and lithium cobaltate, and can prepare ternary electrode materials with different properties by adjusting the proportion of nickel, cobalt and manganese. With the rise and development of new energy automobiles, ternary materials are hot spots of research.

The invention provides a preparation method of a copper-loaded ternary nanoribbon cathode material. Copper can improve the conductivity of the material, and the structure has a large specific surface area and can be fully contacted with electrolyte, so that the electrochemical performance of the material can be improved. And the preparation method is simple, the process conditions are easy to realize, the energy consumption is low, and the preparation is pollution-free.

Disclosure of Invention

In order to overcome the defect of poor electrochemical performance of the ternary material, the invention aims to: provides a preparation method of a copper-loaded ternary nanobelt anode material.

Yet another object of the present invention is to: provides a copper-loaded ternary nanobelt cathode material product obtained by the method.

Yet another object of the present invention is to: provides an application of the product.

The purpose of the invention is realized by the following scheme: a preparation method of a copper-loaded ternary nanoribbon cathode material is used for preparing the copper-loaded ternary nanoribbon cathode material by combining a hydrothermal method and in-situ reduction, and comprises the following steps:

(1) dissolving lithium salt, nickel salt, cobalt salt, manganese salt and 1 mL of nitric acid in deionized water to ensure that the molar weight ratio of the lithium salt, the nickel salt, the cobalt salt and the manganese salt is 1: 1-x-y: x: y, and stirring to obtain a uniform and clear precursor solution; adding the mixed solution into 15 mL of sodium hydroxide alkali solution, moving the mixed solution into a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 180-200 ℃ for 1-3 h; centrifuging a product after reaction, washing precipitates obtained after centrifugation for many times by using deionized water and absolute ethyl alcohol, drying, and grinding by using an agate mortar to obtain a ternary nanobelt anode material;

(2) dissolving 0.005-0.01 mol of copper oxide in deionized water, stirring for 10-20 min, and then dropwise adding 5-10 mL of ammonia water to obtain a solution A; dissolving 5-10 g of sodium dodecyl benzene sulfonate in 50mL of deionized water, and stirring until the solution is transparent to obtain a solution B; dropwise adding the solution B into the solution A, and stirring for 5-10 hours after dropwise adding to obtain a solution C; adding the product obtained in the step (1) into the solution C to obtain a solution D; dropwise adding 2-5 mmol of reducing agent into the solution D, continuously stirring for 3-6 h, washing the obtained precipitate with deionized water and ethanol for several times, carrying out suction filtration, and drying to obtain a final product.

The lithium salt is one or the combination of lithium acetate and lithium nitrate.

The nickel salt is one or the combination of nickel acetate and nickel nitrate.

The cobaltate is one or the combination of cobalt acetate and cobalt nitrate.

The manganate is one or the combination of manganese acetate and manganese nitrate.

The reducing agent is one or the combination of ascorbic acid and sodium borohydride.

The invention also provides a copper-loaded ternary nanoribbon cathode material prepared by any one of the methods.

The invention also provides application of the copper-loaded ternary nanobelt cathode material in a lithium ion battery.

The invention provides a preparation method of a copper-loaded ternary nanoribbon cathode material. Copper can improve the conductivity of the material, and the structure has a large specific surface area and can be fully contacted with electrolyte, so that the electrochemical performance of the material can be improved. And the preparation method is simple, the process conditions are easy to realize, the energy consumption is low, and the preparation is pollution-free.

Drawings

FIG. 1 is LiNi loaded with copper in example 1_1/3Co_1/3Mn_1/3O₂A cycle life plot of the nanoribbons;

FIG. 2 shows LiNi loaded with copper in example 2_0.5Co_0.3Mn_0.2O₂A cycle life plot of the nanoribbons;

FIG. 3 is LiNi loaded with copper according to example 3_0.8Co_0.1Mn_0.1O₂Graph of rate performance of nanobelts.

Detailed Description

The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.