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MnS/carbon composite material with sulfur defect as well as preparation method and application of MnS/carbon composite material

A carbon composite material and defect technology, applied in the direction of structural parts, electrical components, battery electrodes, etc., can solve the problems of large volume change, low restrictions on the application of lithium battery anode materials, low battery cycle life, etc., to improve electronic conductivity, good Electrochemical performance, the effect of improving electrochemical activity

Pending Publication Date: 2022-07-29
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In current research, there are still two major difficulties in using α-MnS as a negative electrode material: (1) Although its own conductivity is higher than that of its oxide analogues, its intrinsic low limits its use as a negative electrode for lithium batteries. Further application of the material
(2) The volume of α-MnS changes greatly during charge and discharge, which may lead to low cycle life of the battery
However, in the prior art, most of the studies on transition metal sulfur defects are based on molybdenum metal, but there are very few studies on manganese metal. Therefore, it is of great significance to prepare rock-salt MnS containing sulfur defects.

Method used

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  • MnS/carbon composite material with sulfur defect as well as preparation method and application of MnS/carbon composite material
  • MnS/carbon composite material with sulfur defect as well as preparation method and application of MnS/carbon composite material
  • MnS/carbon composite material with sulfur defect as well as preparation method and application of MnS/carbon composite material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] First, 10 mg of nitrogen-doped porous carbon spheres were ultrasonically dispersed into 20 mL of water, followed by a certain amount of KMnO 4 (5-20 mg) dissolved therein. After this, the dispersion was transferred to a 50 mL Teflon-lined autoclave for hydrothermal reaction at 140 °C for 1 h. After centrifugation and washing, the obtained solid was heated to 700 °C for 2 h at a heating rate of 5 °C / min and calcined to obtain NMCN@MnO(x) (x=5, 10, 20) nanospheres.

Embodiment 2

[0029] The NMCN@MnO and sublimed sulfur were thoroughly mixed in a mass ratio of 1:1.5 and placed in a corundum boat. Then, put the corundum boat into the tube furnace, in N 2 The temperature was raised to 400 °C for 5 h at a heating rate of 2 °C / min under the atmosphere to realize the conversion of MnO to MnS. Finally, the calcined solid is washed with carbon disulfide to remove residual sulfur to obtain the desired product. Various samples prepared in this case can be represented by the general formula NSMCN@SV-MnS(x), where x represents KMnO 4 The amount of addition (5-20mg).

[0030] like figure 1 The NMCN@MnO(x) materials prepared for Examples 1 and 2 (a, b, c represent x=5, 10, 20, respectively) and NSMCN@SV-MnS(x) (d, e, f represent x, respectively) =5, 10, 20) TEM images. It can be seen from the figure that both the morphologies of the NMCN@MnO(x) material and NSMCN@SV-MnS(x) maintain uniform particles within the porous sphere, and with the increase of the precurs...

Embodiment 3

[0043] 80% of the samples (NSMCN@SV-MnS(x) or NMCN@MnO(10) materials), 10% conductive carbon black were dispersed into 10% PVDF in NMP solution. It was evenly coated on copper foil, and after drying in a vacuum oven for 12 hours, it was punched into a circular electrode sheet with a diameter of 12 mm. The electrode sheet loaded with active material was used as the working electrode, and the copper foil was used as the counter electrode to form a button battery. Electrolyte (1M LiPF6, the solvent is ethylene carbonate / dimethyl carbonate / ethyl methyl carbonate mixed solvent (EC / DEC / EMC) with a volume ratio of 1:1:1), the battery is assembled in an argon-filled glove carried out in the box. The charge and discharge test of the battery is carried out on the ARBIN test system.

[0044] from Figure 6-7 It can be seen from the figure that the electrochemical performance of the manganese sulfide carbon composite is better than that of the manganese oxide carbon composite under the...

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Abstract

The invention relates to a MnS / carbon composite material with sulfur defects and a preparation method and application thereof.The preparation method comprises the steps that N-doped carbon microspheres serve as a template, a certain amount of KMnO4 serves as a precursor, and then a reaction kettle hydrothermal method is used for calcining at the temperature of 700 DEG C under inert gas to obtain a metal oxide carbon composite material with the uniform particle size; and further vulcanizing and calcining to 400 DEG C in an inert atmosphere to form the MnS / carbon composite material. The prepared carbon composite material is a material with rock salt type (alpha-MnS) and rich sulfur defects at the same time, the particle size of the material is controllable, the material has a high specific surface area, meanwhile, the electronic structure of manganese sulfide is modulated due to the generation of sulfur vacancies, so that the composite material has good electrochemical performance, and the composite material can be used as a high-performance lithium battery negative electrode material.

Description

technical field [0001] The invention relates to the technical field of lithium batteries, in particular to a MnS / carbon composite material with sulfur defects, a preparation method and application thereof. Background technique [0002] With the widespread use of electric vehicles in recent years, the battery commercialization market urgently needs an anode material with a theoretical specific capacity higher than that of commercial graphite, abundant natural reserves, environmental friendliness and low cost. In recent years, due to the high theoretical specific capacity of rock-salt MnS (α-MnS) (616mAh g -1 ) and is the most stable of the three crystal forms of MnS (the other two are β and γ phases), and has received great attention in battery materials. In current research, α-MnS still has two major difficulties as a negative electrode material: (1) Although its conductivity is higher than that of its oxide analogs, its intrinsic low limit limits its use as a lithium batte...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/525H01M4/58H01M4/62H01M10/052
CPCH01M4/364H01M4/628H01M4/5815H01M4/625H01M10/052H01M4/525H01M2004/027H01M2004/021
Inventor 韩杰孙思微刘英伟王超王钦超郭荣
Owner YANGZHOU UNIV
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