Method for preparing high-capacity self-supporting manganese dioxide/carbon composite electrode

A manganese dioxide, self-supporting technology, applied in the field of electrochemistry, can solve problems such as poor contact between electrode active materials and current collectors, unfavorable charge balance ion transfer, and affecting electrode charge and discharge performance, so as to optimize electrochemical reaction impedance, High specific capacitance, the effect of improving stability

Active Publication Date: 2017-07-14
CENT SOUTH UNIV
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  • Abstract
  • Description
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Problems solved by technology

However, most of the research is to first prepare carbon / manganese dioxide composite materials in the form of powder, and then mix these powder materials with binders and apply them to current collectors to prepare electrodes, which is easy to cause electrode active substances. Poor contact with the current collector affects the charge and discharge performance of the electrode
In addition, the preparation of manganese dioxide on the surface of different carbon skeletons by electrolysis of manganese sulfate solution to prepare binder-free, self-supporting manganese dioxide / carbon composite electrodes is a current research hotspot, but from the reported situation, The focus of these research work is mainly focused on how to prepare different carbon skeletons, without controlling the structure of manganese dioxide on the surface of carbon skeletons, mainly in the preparation of conventional electrolytic manganese dioxide preparation methods on carbon skeletons. Manganese, that is, mainly through the electrolysis of manganese dioxide aqueous solution at room temperature gamma manganese dioxide
Obviously, since the internal tunnel structure of γ-manganese dioxide is a 1×2 or 1×1 tunnel, this is not conducive to the transfer of charge-balanced ions in the electrode material during charge and discharge, and affects the capacitive performance of the material.

Method used

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  • Method for preparing high-capacity self-supporting manganese dioxide/carbon composite electrode
  • Method for preparing high-capacity self-supporting manganese dioxide/carbon composite electrode

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Formulated with MnSO 4 and CeSO 4 and sulfuric acid mixed aqueous solution, the concentration of manganese sulfate in the mixed solution is 0.5mol / L, the concentration of cerium sulfate is 0.01mol / L, and the concentration of sulfuric acid is 0.5mol / L. Cut the carbon paper into an area of ​​4×1cm 2 The carbon paper tape is used as a current collector, and the current collector is ultrasonically washed with 10% sulfuric acid aqueous solution and acetone in sequence, and finally rinsed with water and dried. Use an area of ​​4×4cm 2The titanium mesh electrode is the counter electrode, the above mixed solution is the electrodeposition solution, and the current collector after surface cleaning is the anode (the working area is 1×1cm 2 ), conduct constant current anodic oxidation electrodeposition, the temperature of the electrodeposition solution is 5°C, and the current density is 4mA / cm 2 , the electrodeposition time is 2 minutes. After the electrodeposition is complete...

Embodiment 2

[0046] The operation process is the same as in Example 1, except that the lanthanum sulfate used replaces cerium sulfate, and the concentration of lanthanum sulfate in the mixed solution is 0.05mol / L, and the concentration of sulfuric acid is 1mol / L. The concentration of lanthanum sulfate in the hydrothermal treatment solution is 0.1mol / L, the hydrothermal treatment temperature is 180°C, and the hydrothermal treatment time is 12 hours to obtain a composite electrode. The Mn in the composite electrode 4+ / Mn 3+ The ratio is 3.7:1;

[0047] The specific capacitance of the obtained electrode active material at 2mV / s is 330.2F / g, and the cyclic voltammetry curve remains approximately rectangular when the scan rate is increased to 200mV, and the capacity retention rate is 64.1%.

Embodiment 3

[0049] The operation process is the same as in Example 1, except that potassium sulfate used replaces cerium sulfate, and the concentration of potassium sulfate in the mixed solution is 0.1mol / L, and the concentration of sulfuric acid is 3mol / L. The concentration of potassium sulfate in the hydrothermal treatment solution is 0.2mol / L, the hydrothermal treatment temperature is 120°C, and the hydrothermal treatment time is 24 hours to obtain a composite electrode. The Mn in the composite electrode 4+ / Mn 3+ The ratio is 4.8:1;

[0050] The specific capacitance of the obtained electrode active material at 2mV / s is 351.2F / g, and the cyclic voltammetry curve remains approximately rectangular when the scan rate is increased to 200mV, and the capacity retention rate is 60.2%.

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Abstract

The invention relates to the technical field of electrochemistry, in particular to a method for preparing a high-capacity self-supporting manganese dioxide/carbon composite electrode. The method comprises the following steps: firstly, dissolving manganese sulfate and a water-soluble structural stabilizer in a sulfuric acid aqueous solution to form a mixed solution, wherein a radius of metal cations in the water-soluble structural stabilizer is (1-1.52)*10<-10>m; then, selecting a carbonaceous material with a clean surface as an anode, and using the mixed solution obtained in step 1 as an electrolyte; performing oxidization on the anode for electrochemical deposition of manganese dioxide at the temperature of 15 DEG C to obtain a semi-finished product, wherein during performing anode oxidization electrochemical deposition, an electric potential of the anode is controlled to be greater than or equal to 0.14 V; and then, placing the semi-finished product into a solution containing the water-soluble structural stabilizer, and performing a hydrothermal reaction at the temperature of 120-200 DEG C to obtain the high-capacity self-supporting manganese dioxide/carbon composite electrode. The method is simple in preparation process, the obtained product is excellent in performance, and industrial production is facilitated.

Description

technical field [0001] The invention belongs to the technical field of electrochemistry, and in particular relates to a preparation method of a high-capacity self-supporting manganese dioxide / carbon composite electrode. [0002] technical background [0003] Supercapacitor is a new concept energy storage device between batteries and traditional electrostatic capacitors. Compared with traditional electrostatic capacitors such as aluminum electrolytic capacitors, supercapacitors have higher specific capacitance, and the energy density that can be stored is traditional electrostatic capacitors Compared with batteries, supercapacitors have greater power density, and have the characteristics of high charge and discharge efficiency and long cycle life. Due to the many advantages above, the development of supercapacitor technology has been widely valued by academia, industry and military departments, and it is gradually being used as a backup power supply for electronic instruments,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01G11/86H01G11/24H01G11/30H01G11/44H01G11/46
CPCY02E60/13H01G11/86H01G11/24H01G11/30H01G11/44H01G11/46
Inventor 陈亚关杰豪甘辉孔令昆陈白珍石西昌
Owner CENT SOUTH UNIV
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