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Preparation method of NCM ternary cathode material doped with Al<3+> on surface

A positive electrode material and surface layer technology, applied in the field of chemical energy storage batteries, can solve problems such as poor electrochemical performance, and achieve the effects of improving reversible discharge capacity, inhibiting mixed discharge, and simple operation

Inactive Publication Date: 2018-06-05
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Doped Al prepared against prior art 3+ The electrochemical performance of the NCM ternary positive electrode material under high voltage and high rate is not good, the object of the present invention is to provide a kind of surface doping Al 3+ The preparation method of the NCM ternary positive electrode material, this method is to carry out Al in the process that the precursor of NCM ternary positive electrode material is mixed with lithium salt 3+ doped, thereby achieving Al 3+ In the doping of the lithium layer in the surface layer of the NCM ternary cathode material, when a large amount of lithium ions are intercalated, Al 3+ The lithium layer can effectively maintain the stability of the lattice structure, retain more reversible lithium sites, and ensure the reversibility of lithium ion intercalation / intercalation, thereby improving the electrochemical performance of NCM ternary cathode materials, especially for high voltage Significant improvement in electrochemical performance at high rates (4.5V, ≥1C)

Method used

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  • Preparation method of NCM ternary cathode material doped with Al&lt;3+&gt; on surface
  • Preparation method of NCM ternary cathode material doped with Al&lt;3+&gt; on surface
  • Preparation method of NCM ternary cathode material doped with Al&lt;3+&gt; on surface

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] LiOH·H 2 O was added into the mortar, and after dry grinding for 15 min, it was mixed with Al(NO 3 ) 3 9H 2 O was sonicated in ethanol for 4 h, then transferred to a mortar and Ni 0.8 co 0.1 mn 0.1 (OH) 2 Powder, after dry milling for 25 minutes, add ethanol and continue grinding for 25 minutes, then place the mixture of the three in an oxygen atmosphere, heat it to 450°C and keep it for 6 hours, then raise the temperature to 750°C and keep it for 12 hours, then cool with the furnace. get doped Al 3+ The NCM ternary cathode material Li 0.99 al 0.01 [Ni 08 co 0.1 mn 0.1 ]O 2 , abbreviated as Al-NCM811; among them, LiOH·H 2 O and Al(NO 3 ) 3 9H 2 The molar ratio of O is 99:1, LiOH·H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio is 1.040:1.

[0035] The Al-NCM811 prepared in Example 1 was used as the positive electrode material to assemble a CR2025 button battery, and the corresponding electrochemical performance tests were carried out.

[0036...

Embodiment 2

[0045] LiOH·H 2 O was added into the mortar, and after dry grinding for 15 min, it was mixed with Al(NO 3 ) 3 9H 2 O was sonicated in ethanol for 4 h, then transferred to a mortar and Ni 0.8 co 0.1 mn 0.1 (OH) 2 Powder, after dry milling for 25 minutes, add ethanol and continue grinding for 25 minutes, then place the mixture of the three in an oxygen atmosphere, heat it to 450°C and keep it for 6 hours, then raise the temperature to 750°C and keep it for 12 hours, then cool with the furnace. get doped Al 3+ The NCM ternary cathode material Li 0.995 al 0.005 [Ni 08 co 0.1 mn 0.1 ]O 2 , abbreviated as Al-NCM811; among them, LiOH·H 2 O and Al(NO 3 ) 3 9H 2 The molar ratio of O is 199:1, LiOH·H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio is 1.045:1.

[0046] The Al-NCM811 prepared in embodiment 2 is assembled into CR2025 button battery as positive electrode material and carries out electrochemical performance test. The constant current charge and dis...

Embodiment 3

[0048] LiOH·H 2 O was added into the mortar, and after dry grinding for 15 min, it was mixed with Al(NO 3 ) 3 9H 2 The O powder was sonicated in ethanol for 4 h, then transferred to a mortar, and Ni 0.8 co 0.1 mn 0.1 (OH) 2 Powder, after dry milling for 25 minutes, add ethanol and continue grinding for 25 minutes, then put the mixture of the three in an oxygen atmosphere, first heat to 450°C and keep it for 6 hours, then raise the temperature to 750°C and keep it for 12 hours, then cool with the furnace, get doped Al 3+ The NCM ternary cathode material Li 0.985 al 0.015 [Ni 08 co 0.1 mn 0.1 ]O 2 , abbreviated as Al-NCM811; among them, LiOH·H 2 O and Al(NO 3 ) 3 9H 2 The molar ratio of O is 65.7:1, LiOH·H 2 O and Ni 0.8 co 0.1 mn 0.1 (OH) 2 The molar ratio is 1.034:1.

[0049] The Al-NCM811 prepared in embodiment 3 is assembled into CR2025 button cell as positive electrode material and carries out electrochemical performance test. The constant current cha...

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Abstract

The invention relates to a preparation method of an NCM ternary cathode material doped with Al<3+> on the surface and belongs to the field of chemical energy storage batteries. The preparation methodprovided by the invention has the benefits that aluminum nitrate is added in the mixing process of a nickel-cobalt-manganese hydroxide precursor and lithium hydroxide to realize the doping of the Al<3+> on a lithium layer on the surface; compared with the situation that the Al<3+> is doped on a transition metal layer in the preparation process of the nickel-cobalt-manganese hydroxide precursor, the Al<3+> exists on the lithium layer and can better play a supporting role, less Al<3+> can be used to achieve a structure stabilizing effect, and particularly, and the improvement effect on electrochemical performance at high voltage and high rate is significant. The preparation method provided by the invention is simple to operate, a process and a technology are easy to realize, the large-scalecommercial application can be realized, and the method can be used for Al<3+> doping on the surface of other ternary cathode materials or a lithium-rich cathode material.

Description

technical field [0001] The invention relates to a method of doping Al on the surface of NCM ternary cathode material 3+ The method belongs 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, environmental pollution has gradually become a key issue of concern to 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 the practical application 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 gradually being replaced by ternary mate...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M4/62H01M10/0525
CPCH01M4/364H01M4/505H01M4/525H01M4/628H01M10/0525Y02E60/10
Inventor 苏岳锋李晴吴锋卢赟陈来包丽颖陈实王敬陈刚杨智茹
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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