阅读说明：本技术 一种氧化锰铜超级电容器电极材料的制备方法 (Preparation method of manganese copper oxide supercapacitor electrode material ) 是由 张希华 李斌 张鹏翔 于 2019-10-23 设计创作，主要内容包括：本发明属于新材料领域,尤其涉及一种氧化锰铜(CuMnO<Sub>2</Sub>)超级电容器电极材料的制备方法。本发明特征是：首先将MnCl<Sub>2</Sub>和CuSO<Sub>4</Sub>的混合溶液加入Na<Sub>2</Sub>SiO<Sub>3</Sub>溶液,得到混合物；然后将混合物搅拌充分,转移到反应釜内衬中,在120-200℃下保温5-10小时；或在80-100℃的油浴锅或电热套中,保温0.5-1小时；得到粉末状的硅酸锰/硅酸铜前驱体材料；再将制备的前驱体材料放入反应釜内衬中,加入NaOH溶液,在160-180℃温度下保温1-24小时；得到粉末状的氧化锰铜材料。本发明操作简单,成本低,便于批量生产；制备的氧化锰铜材料比电容高,工作电压范围大,倍率性能好,具有很好的应用前景。(The invention belongs to the field of new materials, and particularly relates to copper manganese oxide (CuMnO) 2 ) A preparation method of a super capacitor electrode material. The invention is characterized in that: firstly, MnCl is added 2 And CuSO 4 Adding Na into the mixed solution 2 SiO 3 Dissolving to obtain a mixture; then the mixture is fully stirred and transferred into the lining of a reaction kettle, and the temperature is kept for 5 to 10 hours at the temperature of 120-; or keeping the temperature for 0.5 to 1 hour in an oil bath pan or an electric heating sleeve at the temperature of between 80 and 100 ℃; obtaining powdery manganese silicate/copper silicate precursor material; then the prepared precursor material is put into the inner liner of the reaction kettle, NaOH solution is added, and the temperature is kept at 160-180 ℃ for 1-24 hours; obtaining the powdery manganin oxide material. The invention has simple operation, low cost and convenient batch production; prepared manganese oxide copper material specific capacitanceHigh working voltage range, good multiplying power performance and good application prospect.)

1. A preparation method of a manganese copper oxide supercapacitor electrode material is characterized by comprising the following implementation steps:

(1) mixing MnCl₂、CuSO₄Dissolving in deionized water, Na₂SiO₃Dissolving in another part of deionized water; stirring Na₂SiO₃Dissolving, and adding MnCl₂And CuSO₄Adding Na under stirring to the mixed solution₂SiO₃Dissolving to obtain a mixture; MnCl₂，CuSO₄And Na₂SiO₃In a molar ratio of 1:1: 2;

(2) fully stirring the mixture prepared in the step (1), transferring the mixture into a lining of a reaction kettle, and preserving heat for 5-10 hours at the temperature of 120-; or the mixture prepared in the step (1) is fully stirred and is kept warm for 0.5 to 1 hour in an oil bath pan or an electric heating jacket at the temperature of between 80 and 100 ℃; taking out the reaction product, performing suction filtration or centrifugation by using deionized water and absolute ethyl alcohol as a cleaning agent, separating the product, drying, grinding and sieving to obtain a powdery manganese silicate/copper silicate precursor material;

(3) putting the precursor material prepared in the step (2) into a lining of a reaction kettle, and adding 1-4mol L of the precursor material^-1NaOH solution of (2); the reaction kettle is insulated for 1 to 24 hours at the temperature of 160-; and taking the reaction product out of the inner liner of the reaction kettle, performing suction filtration or centrifugation by using deionized water and absolute ethyl alcohol as cleaning agents, separating out precipitates generated in the reaction kettle, and drying, grinding and sieving to obtain the powdery copper manganese oxide material.

Technical Field

The invention belongs to the field of new materials, and particularly relates to copper manganese oxide (CuMnO)₂) A preparation method of a super capacitor electrode material.

Background

The super capacitor has long cycle charge and discharge life, high charge and discharge speed and good environmental adaptability. However, the conventional super capacitor material has a low specific capacitance, and the energy density of the formed device is low, so that the wide application of the energy storage device is limited. The development of electrode materials with high specific capacitance, good rate capability and large working voltage range is an important means for improving the energy storage performance of the super capacitor.

At present, the manganese copper oxide material is mainly applied to the fields of catalysts, light-emitting diodes, fluorescent materials, lithium batteries, supercapacitor electrode materials and the like. The invention with the application number of 201810280842.5 discloses a CuMnO with a manganite structure₂The shape regulating method of crystal material uses surfactant to make solvothermal reaction, and after controlling reaction temp. the powder material with different shapes can be obtained. However, the voltage range of the electrode material obtained by the process is only 0.4V. This method is complicated in steps, and the use of a surfactant causes washing difficulty and increases production costs. The invention patent with application number 201810664573.2 discloses a manganese copper oxide powder and a preparation method thereof, wherein, the precursor is roasted at the temperature of 900-1200 ℃ to obtain the micron-sized manganese copper oxide material. However, the method has complex process and high energy consumption.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides the preparation method of the manganese copper oxide supercapacitor electrode material which is simple in preparation process, low in cost and convenient for batch production, and the prepared material has the characteristics of high specific capacitance, large working voltage range, long cycle life and the like.

The invention is realized by the following modes:

preparation method (CuMnO) of manganese copper oxide supercapacitor electrode material₂) The method is characterized by comprising the following implementation steps:

(1) mixing MnCl₂、CuSO₄Dissolving in deionized water, Na₂SiO₃Dissolving in another part of deionized water; stirring Na₂SiO₃Dissolving, and adding MnCl₂And CuSO₄Adding Na under stirring to the mixed solution₂SiO₃Dissolving to obtain a mixture; MnCl₂，CuSO₄And Na₂SiO₃In a molar ratio of 1:1: 2;

(2) fully stirring the prepared mixture in the step (1), transferring the mixture into a lining of a reaction kettle, and preserving heat for 5-10 hours at the temperature of 120-; or the mixture prepared in the step (1) is fully stirred and is kept warm for 0.5 to 1 hour in an oil bath pan or an electric heating jacket at the temperature of between 80 and 100 ℃; taking out the reaction product, performing suction filtration or centrifugation by using deionized water and absolute ethyl alcohol as a cleaning agent, separating the product, drying, grinding and sieving to obtain a powdery manganese silicate/copper silicate precursor material;

(3) putting the precursor material prepared in the step (2) into the inner liner of a reaction kettle, and adding 1-4mol L of the precursor material^-1NaOH solution of (2); the reaction kettle is insulated for 1 to 24 hours at the temperature of 160-; taking out the reaction product from the inner liner of the reaction kettle, performing suction filtration or centrifugation by using deionized water and absolute ethyl alcohol as cleaning agents, separating out precipitate generated in the reaction kettle, drying, grinding and sieving to obtain powdery copper manganese oxide (CuMnO)₂) A material.

The invention has the beneficial effects that:

(1) the invention overcomes the defects of the traditional process, has simple operation and low cost and is convenient for batch production; the prepared manganese oxide copper material has high specific capacitance, large working voltage range (which can reach 0.6V), good rate capability and good application prospect.

(2) The manganese copper oxide (CuMnO) of the invention₂) The material is used as a positive electrode material, is matched with an active carbon negative electrode material, and is assembled into an asymmetric capacitor device by using a 1M KOH aqueous solution as an electrolyte. At 400W kg^-1The energy density can reach 30.1Wh kg at most under the power density of^-1(ii) a At 24000W kg^-1The energy density can still reach 12.2Wh kg under the high power density^-1. Its long-circulating performance is excellent, and when it is 15000 circles, it still can retain above 90% of initial specific capacitance.

Detailed Description

Four preferred embodiments of the present invention are given below, but the present invention is not limited thereto.