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Alpha-MnO2/carbon composite electrode material and preparation method and application thereof

An electrode material, carbon composite technology, applied in battery electrodes, circuits, electrical components, etc., can solve problems such as limiting the energy density of the full battery, low tap density, and poor electrochemical performance.

Active Publication Date: 2020-07-07
浙江浙能中科储能科技有限公司
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  • Application Information

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Problems solved by technology

But nanoscale α-MnO 2 The preparation process of the material is not only complicated, but also generally has a low tap density, so that the prepared positive electrode sheet has a low active material loading per unit area, which limits the improvement of the energy density of the full battery.
Pan (Pan, H.L.; Shao, Y.Y.; Yan, P.F.; Cheng, Y.W.; Han, K.S.; Nie, Z.M.; Wang, C.M.; Yang, J.H.; Li, X.L.; Bhattacharya, P.; Mueller, K.T.; Liu, J. .Nature Energy 2016,1,(5),16039.) et al prepared nano-α-MnO with good crystallization properties by hydrothermal method 2 materials, applied in water-based zinc-ion batteries to obtain higher rate performance, but the preparation method is cumbersome and needs to be carried out in a high-temperature, high-pressure reactor, and it is difficult to prepare in batches
At the same time, the manganese dioxide material itself has poor conductivity. When it is used as a zinc ion electrode material, it cannot provide a relatively fast electron transmission channel during the charge and discharge process at a large rate, which makes the high rate cycle performance poor.
An Junwei et al. (Patent Document 2: Chinese Publication No. CN105047419A) prepared a manganese dioxide nanosheet / carbon black particle composite structure material by hydrothermal reaction, and applied it in a supercapacitor, showing a good Electrochemical performance, but its preparation method still uses hydrothermal reaction, which is not conducive to large-scale industrial synthesis
Mou Jian et al. (α-MnO 2 In Zn|ZnSO 4 |MnO 2 Research on the discharge mechanism in [J]; Contemporary Chemical Industry; 2018 Issue 08) introduced a liquid phase reaction method to prepare α-MnO 2 However, the homogeneity of the prepared manganese dioxide product is poor, and the crystallization property of the product after heat treatment is poor, which affects the electrochemical activity of the material
At the same time, the obtained precursor product is not compounded with carbon materials, resulting in poor electrochemical performance of the product, and the charge-discharge specific capacity is lower than 200mAh g -1 , and poor cycle stability

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Effect test

Embodiment 1

[0042] (1) The potassium permanganate that takes by weighing 0.3mol is dissolved in the deionized water of 1L, disperses evenly, and is recorded as solution A; In addition, the manganese sulfate of 0.5mol and the sodium carbonate of 0.4mol are dissolved in the deionized water of 2L, Evenly dispersed, recorded as solution B. Solutions A and B were dispersed using an emulsification disperser, while solution A was added dropwise (1 ml / sec) into solution B. After the reaction is complete, the reacted mixed solution is left to stand for 12 hours, the precipitate is suction filtered and washed, and the resulting precipitated product is collected;

[0043] (2) The precipitated product of step (1) was dried in an oven at 110°C for 10 hours to obtain nano-spherical α-MnO 2 The precursor powder of the material, with figure 1 The SEM picture of its microstructure, it can be seen from the picture that the material has good dispersion performance, is nano-spherical (between 50 and 100nm)...

Embodiment 2

[0047] (1) Weigh 0.4mol of potassium permanganate and dissolve it in 2L of deionized water, disperse evenly, and record it as solution A; in addition, weigh 0.6mol of manganese chloride and 0.7mol of sodium carbonate and dissolve it in 2L of deionized water , dispersed evenly, recorded as solution B. Solutions A and B were dispersed using an emulsification disperser, while solution B was added dropwise (0.5 ml / sec) into solution A. After the reaction is complete, the reacted mixed solution is left to stand for 16 hours, the precipitate is suction filtered and washed, and the resulting precipitated product is collected;

[0048] (2) Place the precipitated product of step (1) in an oven at 105°C and dry for 12 hours to obtain nano-spherical α-MnO 2 The precursor powder of the material;

[0049] (3) 8g of nano-spherical α-MnO obtained in step (2) 2 Mix the precursor powder with 1.5g graphene, 0.2g graphite, and 0.6g of 50wt% polyacrylic acid aqueous solution, and add 150g deio...

Embodiment 3

[0053](1) Take 0.1mol of potassium permanganate and dissolve it in 1L of deionized water, disperse evenly, and record it as solution A; in addition, weigh 0.2mol of manganese nitrate and 0.4mol of potassium carbonate and dissolve it in 1L of deionized water, Evenly dispersed, recorded as solution B. Solutions A and B were dispersed using an emulsification disperser, while solution A was added dropwise (3 ml / sec) into solution B. After the reaction is complete, the reacted mixed solution is left to stand for 24 hours, the precipitate is suction filtered and washed, and the resulting precipitated product is collected;

[0054] (2) Place the precipitated product of step (1) in an oven at 108°C and dry for 24 hours to obtain nano-spherical α-MnO 2 The precursor powder of the material;

[0055] (3) 7g of nano-spherical α-MnO obtained in step (2) 2 Mix the precursor powder with 2g acetylene black, 0.6g graphite, and 0.8g of 50wt% polyacrylic acid aqueous solution, and add 200g de...

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Abstract

The invention relates to an alpha-MnO2 / carbon composite electrode material and a preparation method and application thereof. The preparation method of the alpha-MnO2 / carbon composite electrode material comprises the steps of (1) mixing a potassium permanganate aqueous solution with an aqueous solution containing a low-valence manganese salt and an acid-base regulator, carrying out a co-precipitation reaction at room temperature, filtering, and drying to obtain precursor powder; (2) mixing the obtained precursor powder, a carbon material, a dispersing agent and a solvent, and performing spray granulation to obtain granulated powder; and (3) carrying out heat treatment on the obtained granulated powder at the temperature of 300-600 DEG C to obtain the alpha-MnO2 / carbon composite electrode material.

Description

technical field [0001] The present invention relates to a kind of α-MnO with excellent crystallization properties 2 The invention discloses a carbon / carbon composite electrode material, a preparation method thereof, and an application in a positive electrode of a zinc ion battery, belonging to the technical field of zinc ion batteries. Background technique [0002] Manganese dioxide has a unique three-dimensional pore structure, excellent physical and chemical properties, low price, and environmental friendliness. As an important functional material, it is widely used in catalysts, adsorbents, ceramics, and battery electrode materials. In order to meet people's growing demand for energy storage materials, manganese dioxide materials have great application potential in the field of energy storage devices such as batteries and supercapacitors due to their unique advantages. [0003] In recent years, research hotspots have focused on rechargeable neutral aqueous zinc / MnO 2 Ba...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/583H01M4/62H01M4/505H01M10/054
CPCH01M4/362H01M4/505H01M4/583H01M4/625H01M10/054Y02E60/10
Inventor 刘宇刘云召秦刚华杜月秀黄佳琪林兴灏李卓斌郑渭建
Owner 浙江浙能中科储能科技有限公司