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La<3+>, Co<3+>, Fe<3+> and F<-1> co-doped composite lithium-rich positive material and preparation method thereof

A lithium-rich positive electrode material and co-doping technology, applied in battery electrodes, electrical components, circuits, etc., can solve problems such as incomplete understanding of the mechanism of action, achieve expanded intercalation and deintercalation channels, good cycle capacity retention, and reduce irreversible The effect of capacity loss

Inactive Publication Date: 2013-05-15
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The mechanism of doping lithium ions on the electrochemical performance of materials is not yet fully understood

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Example 1: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 O:La(NO 3 ) 3 ·6H 2 O:Fe(NO 3 ) 3 9H 2 O: Co(NO 3 ) 2 ·6H 2 O: LiF is 1.082: 0.5365: 0.4365: 0.009: 0.009: 0.009: 0.009 (molar ratio) ratio is evenly mixed, joins in deionized water, the amount of substance added is the tartaric acid that the total amount of all metal ions is 1.2 times fully stirs to Dissolve completely; raise the temperature of the system to 70°C and continue to stir until 71% of the water evaporates, at this time the solution gradually becomes viscous and forms a jelly. The jelly-like substance was dried in an oven at 150° C. for 22 hours and then ground in a mortar for 10 minutes. The obtained powder was heated up to 500°C at a rate of 2°C / min in a tube furnace and calcined at this temperature for 3 hours. After cooling, the powder was taken out and continued to grind in a mortar for 10 minutes, and the powder was pressed with a pressure of 100MPa. After being formed into a ...

Embodiment 2

[0014] Example 2: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 O:La(NO 3 ) 3 ·6H 2 O:Fe(NO 3 ) 3 9H 2 O: Co(NO 3 ) 2 ·6H 2 O: LiF is 1.44: 0.7125: 0.2125: 0.025: 0.025: 0.025: 0.03 (molar ratio) ratio is evenly mixed, joins in deionized water, the amount of substance added is the tartaric acid that all metal ions total amount 1.8 times fully stirs to Completely dissolve; raise the temperature of the system to 90°C and continue to stir until 85% of the water evaporates, at this time the solution gradually becomes viscous and forms a jelly. The jelly-like mass was dried in an oven at 200° C. for 48 hours and then ground in a mortar for 30 minutes. The obtained powder was heated up to 600°C at a rate of 10°C / min in a tube furnace and calcined at this temperature for 6 hours. After cooling, the powder was taken out and continued to grind in a mortar for 30 minutes, and the powder was pressed with a pressure of 300MPa. It was formed into a sheet, and then calci...

Embodiment 3

[0015] Embodiment 3: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 O:La(NO 3 ) 3 ·6H 2 O:Fe(NO 3 ) 3 9H 2 O: Co(NO 3 ) 2 ·6H 2 O: LiF is 1.152: 0.576: 0.376: 0.016: 0.016: 0.016: 0.024 (molar ratio) ratio is evenly mixed, joins in deionized water, the amount of substance added is the tartaric acid that the amount of all metal ions is 1.6 times fully stirs to Dissolve completely; raise the temperature of the system to 80°C and continue to stir until 78% of the water evaporates, then the solution gradually becomes viscous and forms a jelly. The jelly-like mass was dried in an oven at 170° C. for 35 hours and then ground in a mortar for 20 minutes. The obtained powder was heated up to 550°C at a rate of 7°C / min in a tube furnace and calcined at this temperature for 4 hours. After cooling, the powder was taken out and continued to grind in a mortar for 20 minutes, and the powder was pressed with a pressure of 200MPa. After being formed into a sheet, the tempera...

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Abstract

The invention discloses an La<3+>, Co<3+>, Fe<3+> and F<-1> co-doped layer-by-layer composite lithium-rich positive material xLi2MnO3.[1-x]LiMn0.5Ni0.5O2 (x is smaller than or equal to 0.5 and greater than or equal to 0). The La<3+>, Co<3+>, Fe<3+> and F<-1> co-doped layer-by-layer composite lithium-rich anode material is characterized in that the stoichiometric equation is xLi2MnO3.[1-x]Lil-y(Mn0.5Ni0.5)[1-m-n-p]ComLanFepO2-yFy, wherein x is smaller than or equal to 0.5 and greater than or equal to 0; m is smaller than or equal to 0.05 and greater than or equal to 0.01; n is smaller than or equal to 0.05 and greater than or equal to 0.01; p is smaller than or equal to 0.05 and greater than or equal to 0.01; and y is smaller than or equal to 0.06 and greater than or equal to 0.01. The method comprises the steps of adding soluble lithium compound, soluble manganese salt, soluble nickel salt, La(NO3)3.6H2O, Co(NO3)2.6H2O, soluble ferric salt, and lithium fluoride into deionized water according to the stoichiometric proportion of the molecular formula; adding tartaric acid which is 1.2-2.0fold of total mass of all metal ions to fully and evenly agitate until the tartaric acid is completely dissolved; and concentrating, condensing, drying, grinding, decomposing, pressing and burning the solution to obtain the positive material. The prepared positive material has excellent circulation capacity keeping ability and ratio characteristics.

Description

technical field [0001] The invention relates to the field of manufacturing positive electrode materials of lithium ion batteries. Background technique [0002] Lithium-ion batteries have absolute advantages such as high volume, high weight-to-energy ratio, high voltage, low self-discharge rate, no memory effect, long cycle life, and high power density. They have an annual share of more than 30 billion US dollars in the global mobile power market and far exceed other The market share of batteries is the most promising chemical power source [Wu Yuping, Wan Chunrong, Jiang Changyin, Lithium-ion Secondary Batteries, Beijing: Chemical Industry Press, 2002.]. However, since the commercialization of lithium-ion batteries in 1991, the actual specific capacity of cathode materials has always hovered between 100-180mAh / g, and the low specific capacity of cathode materials has become a bottleneck for improving the specific energy of lithium-ion batteries. In order to effectively incre...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525
CPCY02E60/122Y02E60/10
Inventor 汪卓彬水淼杨天赐舒杰冯琳任元龙郑卫东高珊徐晓萍
Owner NINGBO UNIV
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