阅读说明：本技术 一种复合有氧酸水热法改性活性炭电极材料的方法 (Method for modifying active carbon electrode material by composite aerobic acid hydrothermal method ) 是由 张忠洁 万彭 陈鹏鹏 毛昌杰 吴明元 于 2019-09-20 设计创作，主要内容包括：一种复合有氧酸水热法改性活性炭电极材料的方法,包括以下步骤：(1)活性炭预处理；(2)共振声混合；(3)配置有氧酸溶液；(4)水热法釜反应；(5)微波和光复合催化反应；(6)清洗和干燥。本发明利用硫酸、磷酸、乳酸等复合有氧酸的双氧水溶液,依次通过水热法釜反应、微波和光复合催化反应,改性纳米级活性炭；通过红外光谱分析,在活性炭表面形成多种官能团,官能团包括O-H键、C=O双键、C=C双键、C-H键等。(A method for modifying an activated carbon electrode material by an aerobic acid hydrothermal method comprises the following steps: (1) pretreating active carbon; (2) resonant sound mixing; (3) preparing an aerobic solution; (4) carrying out hydrothermal kettle reaction; (5) microwave and light composite catalytic reaction; (6) and (4) cleaning and drying. The invention utilizes hydrogen peroxide solution of sulfuric acid, phosphoric acid, lactic acid and other composite aerobic acids to modify nanoscale active carbon through hydrothermal kettle reaction and microwave and light composite catalytic reaction in sequence; by infrared spectroscopic analysis, various functional groups including an O — H bond, a C = O double bond, a C = C double bond, a C-H bond, and the like are formed on the surface of the activated carbon.)

1. A method for modifying an activated carbon electrode material by a composite aerobic acid hydrothermal method is characterized by comprising the following steps: comprises the following steps:

Step 1: crushing the activated carbon powder to 500-750nm to obtain nano-grade activated carbon for later use;

Step 2: placing the nano-grade activated carbon and absolute ethyl alcohol into a resonance acoustic mixer, and processing for 240-360 seconds under the conditions of frequency of 80-120Hz and amplitude of 1.5-2.0mm to obtain a mixture for later use;

And step 3: mixing the mixture and the aerobic acid solution, putting the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and reacting for 5-7 hours at the temperature of 40-80 ℃; the aerobic acid solution is prepared by uniformly mixing sulfuric acid, phosphoric acid, lactic acid and hydrogen peroxide;

And 4, step 4: placing the reaction material obtained in the step (3) in a composite environment of microwave and illumination, wherein the microwave frequency is 3.0GHz and the power density is 0.40-0.50w/cm²treating for 5-8min with illumination intensity of 35-50 ten thousand Lx;

And 5: carrying out solid-liquid separation on the reaction material obtained in the step (4), and collecting a solid material; washing the solid material with purified water and absolute ethyl alcohol; and then drying, collecting the dried solid material, and grinding into powder to obtain the modified activated carbon electrode material.

2. The method for modifying the activated carbon electrode material by the aerobic hydrothermal method in combination with the method as claimed in claim 1, wherein the method comprises the following steps: the activated carbon is plant type activated carbon, meets the II-grade requirement of the activated carbon for GB/T37386 super capacitors, has the water content of 5-7 percent and the specific surface area of 1500-1800m²/g。

3. The method for modifying the activated carbon electrode material by the aerobic hydrothermal method in combination with the method as claimed in claim 1, wherein the method comprises the following steps: the mass ratio of the nano-grade active carbon to the absolute ethyl alcohol is 100: 120-150.

4. The method for modifying the activated carbon electrode material by the aerobic hydrothermal method in combination with the method as claimed in claim 1, wherein the method comprises the following steps: the mass ratio of the mixture to the aerobic acid solution is as follows: 1: 20-25.

5. The method for modifying the activated carbon electrode material by the aerobic hydrothermal method in combination with the method as claimed in claim 1, wherein the method comprises the following steps: in the aerobic acid solution, the mass fraction of sulfuric acid is 45-55%, the mass fraction of phosphoric acid is 85-90%, the mass fraction of lactic acid is greater than or equal to 98%, and the mass fraction of hydrogen peroxide is 30%; the mass ratio of the sulfuric acid to the phosphoric acid to the lactic acid to the hydrogen peroxide is 1: 1.8-2.2: 1.8-2.2: 90-100.

Technical Field

The invention belongs to the technical field of electrode material preparation, and relates to a method for modifying an activated carbon electrode material by a composite aerobic acid hydrothermal method.

background

The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of quick charge and discharge of the capacitor and the energy storage characteristic of the battery. Compared with a storage battery and a traditional physical capacitor, the super capacitor has the advantages of high power density, long cycle life, wide working temperature limit, no maintenance, environmental protection and the like. A supercapacitor is a novel device for rapidly storing and releasing charges through an interfacial double layer formed between an electrode and an electrolyte. The electrode material is one of the main factors determining the performance of the supercapacitor.

The types of supercapacitors can be classified into electric double layer capacitors, faraday's quasicapacitors (also called pseudo-capacitive capacitors) and hybrid capacitors combining the two, according to their operating principles. The electric double layer capacitor stores energy using interfacial electric double layer capacitance formed between an electrode and an electrolyte based on the theory of an electric double layer. The faraday pseudocapacitors are then based on the faraday process, i.e. they are generated during the electrochemical change of the faraday charge transfer, not only at the surface of the electrode, but also deep inside the electrode. Therefore, the electrode material is one of the main factors determining the performance of the supercapacitor regardless of the type of the supercapacitor. According to these two principles, the electrode materials currently used as supercapacitors are mainly classified into three categories: carbon materials, metal oxides and hydrate materials, conductive polymer materials.

activated Carbon (AC) is the earliest carbon electrode material adopted by a super capacitor, and has the advantages of low cost, excellent conductivity, large specific surface area and the like. However, the activated carbon has the disadvantages of low energy density, small specific capacitance and the like, so that the wide application of the activated carbon is limited to a certain extent, and the activated carbon needs to be subjected to surface modification. The pore size distribution, the specific surface area and the surface groups are important factors for determining the electrochemical performance of the activated carbon material, and therefore, the pore size distribution, the specific surface area and the surface groups are also evaluation indexes of the surface modification effect of the activated carbon.

Disclosure of Invention

The invention aims to provide a method for modifying an activated carbon electrode material by a composite aerobic acid hydrothermal method.

In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a method for modifying an activated carbon electrode material by a composite aerobic acid hydrothermal method comprises the following steps:

step 1: crushing the activated carbon powder to 500-750nm to obtain nano-grade activated carbon for later use;

step 2: placing the nano-grade activated carbon and absolute ethyl alcohol into a resonance acoustic mixer, and processing for 240-360 seconds under the conditions of frequency of 80-120Hz and amplitude of 1.5-2.0mm to obtain a mixture for later use;

And step 3: mixing the mixture and the aerobic acid solution, putting the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and reacting for 5-7 hours at the temperature of 40-80 ℃; the aerobic acid solution is prepared by uniformly mixing sulfuric acid, phosphoric acid, lactic acid and hydrogen peroxide;

And 4, step 4: placing the reaction material obtained in the step (3) in a composite environment of microwave and illumination, wherein the microwave frequency is 3.0GHz and the power density is 0.40-0.50w/cm²Treating for 5-8min with illumination intensity of 35-50 ten thousand Lx;

and 5: carrying out solid-liquid separation on the reaction material obtained in the step (4), and collecting a solid material; washing the solid material with purified water and absolute ethyl alcohol; and then drying, collecting the dried solid material, and grinding into powder to obtain the modified activated carbon electrode material.

The preferable technical scheme is as follows: the activated carbon is plant type activated carbon, meets the II-grade requirement of the activated carbon for GB/T37386 super capacitors, has the water content of 5-7 percent and the specific surface area of 1500-1800m²/g。

the preferable technical scheme is as follows: the mass ratio of the nano-grade active carbon to the absolute ethyl alcohol is 100: 120-150.

The preferable technical scheme is as follows: the mass ratio of the mixture to the aerobic acid solution is as follows: 1: 20-25;

The preferable technical scheme is as follows: in the aerobic acid solution, the mass fraction of sulfuric acid is 45-55%, the mass fraction of phosphoric acid is 85-90%, the mass fraction of lactic acid is greater than or equal to 98%, and the mass fraction of hydrogen peroxide is 30%; the mass ratio of the sulfuric acid to the phosphoric acid to the lactic acid to the hydrogen peroxide is 1: 1.8-2.2: 1.8-2.2: 90-100.

Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:

1. The invention adopts a resonance sound mixing mode to uniformly mix the nano-grade active carbon and the absolute ethyl alcohol with high efficiency, thereby obviously improving the speed and the effect of the subsequent modification reaction.

2. the invention utilizes hydrogen peroxide solution of sulfuric acid, phosphoric acid, lactic acid and other composite aerobic acids to modify nanoscale active carbon through hydrothermal kettle reaction and microwave and light composite catalytic reaction in sequence; by infrared spectroscopic analysis, various functional groups including an O — H bond, a C = O double bond, a C = C double bond, a C-H bond, and the like are formed on the surface of the activated carbon.

3. The functional groups on the surface of the modified activated carbon increase the polarity, the wettability and the hydrophilicity of the carbon surface, improve the adsorption of the electrolyte ions on the carbon surface, and increase the effective area for forming a double electric layer, thereby increasing the specific capacitance of the activated carbon electrode material and optimizing the electrochemical performance of the activated carbon electrode material.

4. The oxygen-containing functional groups on the surface of the modified activated carbon can generate pseudo capacitance in a mode of reversible redox reaction, and the capacitance is also synergistically increased.

drawings

FIG. 1 shows the infrared spectrum of AC-H60 measured by the performance test of modified activated carbon material.

FIG. 2 shows that the CV curves of the AC-H40, AC-H60 and AC-H80 electrodes are obtained by testing AC-H40, AC-H60 and AC-H80 by cyclic voltammetry at a scanning voltage of-1 to 0V and a scanning rate of 100 mV/s.

Detailed Description

The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.

Please refer to fig. 1-2. It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions under which the present invention can be implemented, so that the present invention has no technical significance, and any structural modification, ratio relationship change, or size adjustment should still fall within the scope of the present invention without affecting the efficacy and the achievable purpose of the present invention. In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.