Modified lithium-rich manganese-based anode material and preparation method thereof

A lithium-rich manganese-based, positive electrode material technology, applied in the direction of battery electrodes, electrical components, electrochemical generators, etc., can solve the problems of undeveloped improvement, achieve the effect of simple and easy to control, reduce oxygen evolution of materials, and low cost

Inactive Publication Date: 2019-02-05
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Existing technologies for doping and modifying lithium-rich manganese-based materials are all focused on the use of hetero ions on lithium-rich manganese-based solid solutions (xLi 2 MnO 3 ·(1-x)LiMO 2 ) material, the purpose is

Method used

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  • Modified lithium-rich manganese-based anode material and preparation method thereof
  • Modified lithium-rich manganese-based anode material and preparation method thereof
  • Modified lithium-rich manganese-based anode material and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] The chemical formula of the modified lithium-rich manganese-based positive electrode material is: Li 2 mn 0.5 V 0.5 o 2 F, the valence of the V element is +4, and the valence of the Mn element is +2.

[0037] Depend on figure 1 It can be seen that the Li 2 mn 0.5 V 0.5 o 2 The main diffraction peak of F and Li 2 MnO 3 The main peaks of the standard card 73-0152 overlap, proving that the synthesized material structure and Li 2 MnO 3 similar, and the Li 2 mn 0.5 V 0.5 o 2 The experimental results of the ICP-AES element content of F are consistent with the design target value, as shown in Table 1.

[0038] Depend on figure 2 It can be seen that the Li 2 mn 0.5 V 0.5 o 2 F is a spherical particle with a particle diameter of 200-300nm.

Embodiment 1-1

[0040] (1) 1.42g (0.02mol) of manganese oxide, 1.66g (0.02mol) of vanadium dioxide, 1.04g (0.04mol) of lithium fluoride and 0.62g (0.0208mol) of lithium oxide (2% excess lithium compared to the theoretical amount) ) is uniformly mixed in a solid state to obtain mixture A;

[0041] (2) The mixture A obtained in step (1) is placed in a planetary ball mill under a protective atmosphere of high-purity argon, and ball milled for 24 hours at a revolution speed of 300r / min and an autorotation speed of 600r / min to obtain a modified Lithium-rich manganese-based cathode material Li 2 mn 0.5 V 0.5 o 2 F.

[0042] Battery assembly: the gained 2g Li of the embodiment of the present invention 2 mn 0.5 V 0.5 o 2 F is used as the positive electrode, and 0.25g conductive agent Super-P and 0.25g binder polyvinylidene fluoride are placed in N-methylpyrrolidone solvent dispersant, and mixed into a homogeneous slurry by using a high-speed homogenizer. The micron-scale adjustable membrane ...

Embodiment 1-2

[0046] (1) 2.86g (0.02mol) manganese oxalate, 1.66g (0.02mol) vanadium dioxide, 1.04g (0.04mol) lithium fluoride and 2.80g (0.0424mol) lithium acetate (3% excess lithium compared to theoretical ), mixed uniformly in a liquid phase with a mass ratio of total solids to ethanol of 1:1 to obtain mixture A;

[0047] (2) The mixture A obtained in step (1) is placed in a muffle furnace under the protective atmosphere of high-purity nitrogen gas, and the temperature is raised to 600 °C at a rate of 6 °C / min, and pre-calcined for 4 hours, and then in high-purity nitrogen gas Under a protective atmosphere, place it in a planetary ball mill, and perform ball milling at a revolution speed of 300r / min and an autorotation speed of 600r / min for 24 hours to obtain the lithium-rich manganese-based positive electrode material Li 2 mn 0.5 V 0.5 o 2 F.

[0048] Battery assembly: same as Example 1-1.

[0049] After testing, the lithium-rich manganese-based positive electrode material Li obtai...

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Abstract

The invention discloses a modified lithium-rich manganese-based anode material and a preparation method thereof. The chemical formula of the anode material is Li2MnxM1-xO2F, wherein x is greater thanor equal to 0.5 and less than or equal to 1, and M is a doping element and comprises one or more of Zr, Si, Ge, Sn, V, As, Sb, Cr, Mo, Se or Te. The preparation method comprises the following steps that (1) a manganese source, a doping element source, a fluorine source and an excessive amount of lithium source are uniformly mixed according to the stoichiometric ratio; and (2) ball milling is carried out in a protective atmosphere so as to obtain the anode material. The anode material has the advantages of being high in discharge gram volume, high in coulombic efficiency, stable in material structure and good in cycling performance; and the discharge gram volume of an assembled battery reaches up to 278.0 mAh/g at 22 mA/g and 2.0-4.6 V, and the capacity retention rate reaches up to 93.6% at110 mA/g and 2.5-4.4 V after the assembled battery is circulated for 200 circles. The method has the advantages of being simple, low in cost and suitable for industrial production.

Description

technical field [0001] The invention relates to a positive electrode material and a preparation method thereof, in particular to a modified lithium-rich manganese-based positive electrode material and a preparation method thereof. Background technique [0002] Lithium-ion batteries have the advantages of no memory effect, high safety, high specific energy, and low self-discharge rate, and are widely used in mobile devices, power batteries, and energy storage systems. At present, power batteries face problems such as short cruising range, poor cycle performance and insufficient safety, which seriously restrict their rapid development and application. In recent years, the specific discharge capacity of lithium-rich manganese-based cathode materials has reached 300mAh / g, and its energy density can exceed 300Wh / kg, which is regarded as an ideal choice for the next generation of power lithium batteries. However, lithium-rich manganese-based cathode materials have disadvantages s...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/505H01M4/62H01M10/0525
CPCH01M4/364H01M4/505H01M4/628H01M10/0525Y02E60/10
Inventor 郑俊超范鑫铭张宝刘洋杨舒淇林可博
Owner CENT SOUTH UNIV
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