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Preparation method of NCM ternary positive electrode material with La3+ doped on surface layer

A cathode material and surface layer technology, which is applied in the field of preparation of NCM ternary cathode materials, can solve problems such as unstable surface layer structure, and achieve the effects of low price, simple operation process, and easy process and technology.

Inactive Publication Date: 2018-06-08
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Aiming at the problem that the surface layer structure of the NCM ternary cathode material is unstable during the cycle, the object of the present invention is to provide a surface layer doped La 3+ The preparation method of the NCM ternary positive electrode material, the method is to carry out La in the process of mixing the precursor of the NCM ternary positive electrode material and lithium salt 3+ doped, doped La 3+ Enter the transition metal layer on the surface and occupy Ni 2+ position, which can act as a supporting frame, inhibit the phase transition of the surface structure, and inhibit the Li + / Ni 2+ The effect of mixing can significantly improve the electrochemical performance of NCM ternary cathode materials at high voltage and high rate (4.5V, ≥1C)

Method used

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  • Preparation method of NCM ternary positive electrode material with La3+ doped on surface layer
  • Preparation method of NCM ternary positive electrode material with La3+ doped on surface layer
  • Preparation method of NCM ternary positive electrode material with La3+ doped on surface layer

Examples

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Effect test

Embodiment 1

[0035] LiOH·H 2 O was added to the mortar, and after dry grinding for 15 min, it was mixed with Ni 0.8 co 0.1 mn 0.1 (OH) 2 and La(NO 3 ) 3 ·6H 2 O was ultrasonicated in ethanol for 1.5h, and then the ultrasonicated mixture was transferred to a mortar, dry-milled for 25min, then added with ethanol and continued to be milled for 25min, then the wet-milled mixture was placed in an oxygen atmosphere, and heated to 450 ℃ and keep it for 6 hours, then raise the temperature to 750 ℃ ​​and keep it for 12 hours, then cool down with the furnace to get the surface layer doped La 3+ The NCM ternary cathode material Li[Ni 0.79 co 0.1 mn 0.1 La 0.01 ]O 2 , abbreviated as La-NCM811; among them, LiOH·H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio of La(NO 3 ) 3 ·6H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio of nickel ions in the medium is 1:79.

[0036] The La-NCM811 prepared in Example 1 was used as the positive electrode material to assemble a CR2025...

Embodiment 2

[0047] LiOH·H 2 O was added to the mortar, and after dry grinding for 15 min, it was mixed with Ni 0.8 co 0.1 mn 0.1 (OH) 2 and La(NO 3 ) 3 ·6H 2 O was sonicated in ethanol for 2 hours, and then the sonicated mixture was transferred to a mortar, dry-milled for 25 minutes, then added with ethanol and continued to grind for 25 minutes, then the wet-milled mixture was placed in an oxygen atmosphere, and heated to 450 °C And keep it warm for 6 hours, then raise the temperature to 750°C and keep it warm for 12 hours, and cool down with the furnace to get the surface layer doped La 3+ The NCM ternary cathode material Li[Ni 0.795 co 0.1 mn 0.1 La 0.005 ]O 2 , abbreviated as La-NCM811; among them, LiOH·H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio of La(NO 3 ) 3 ·6H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio of nickel ions in the medium is 1:159.

[0048] The La-NCM811 prepared in Example 2 was used as the positive electrode material to assembl...

Embodiment 3

[0050] LiOH·H 2 O was added to the mortar, and after dry grinding for 15 min, it was mixed with Ni 0.8 co 0.1 mn 0.1 (OH) 2 and La(NO 3 ) 3 ·6H 2 O was sonicated in ethanol for 2 hours, and then the sonicated mixture was transferred to a mortar, dry-milled for 25 minutes, then added with ethanol and continued to grind for 25 minutes, then the wet-milled mixture was placed in an oxygen atmosphere, and heated to 450 °C And keep it warm for 6 hours, then raise the temperature to 750°C and keep it warm for 12 hours, and cool down with the furnace to get the surface layer doped La 3+ The NCM ternary cathode material Li[Ni 0.785 co 0.1 mn 0.1 La 0.015 ]O 2 , abbreviated as La-NCM811; among them, LiOH·H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio of La(NO 3 ) 3 ·6H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio of nickel ions in the medium is 1:52.3.

[0051] The La-NCM811 prepared in Example 3 was used as the positive electrode material to assemb...

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Abstract

The invention relates to a preparation method of an NCM ternary positive electrode material with La3+ doped on a surface layer, belonging to the field of chemical energy storage batteries. According to the method of the invention, La3+ is doped in the process of mixing a nickel cobalt manganese hydroxide precursor with the lithium salt, and the doped La3+ enters a transition metal layer of the surface layer to occupy the position of Ni2+ and can play roles in supporting the framework, suppressing the phase change of the surface layer structure and suppressing the mixed arrangement of Li+ / Ni2+;in addition, La3+ has a relatively large ionic radius, and after La3+ is doped to enter the transition metal layer, a channel for embedding and extraction of Li+ can be widened, the transmission rateof Li+ can be improved, and the electrochemical performance of the NCM ternary positive electrode material at high voltage and high magnification (4.5V, greater than or equal to 1C) can be significantly improved.

Description

technical field [0001] The invention relates to a surface doped La 3+ The invention discloses a preparation method of an NCM ternary cathode material, belonging to the field of chemical energy storage batteries. Background technique [0002] At present, fossil energy sources such as coal, oil, and natural gas are increasingly depleted. In addition, the problem of environmental pollution has gradually become the focus of attention of all countries. The development of pure electric vehicles and gasoline-gas hybrid vehicles has attracted more and more attention. This requires the rapid development of lithium secondary batteries to meet people's urgent needs for practical applications of new energy batteries. In the family of lithium secondary batteries, lithium cobalt oxide, lithium iron phosphate and ternary materials play an important role in the market in turn. Lithium cobalt oxide is mostly used in small portable electronic devices, while lithium iron phosphate is gradua...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M4/485H01M4/62H01M10/0525
CPCH01M4/362H01M4/485H01M4/505H01M4/525H01M4/628H01M10/0525Y02E60/10
Inventor 苏岳锋李晴吴锋卢赟陈来包丽颖陈实王敬张其雨
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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