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Cr3<+>, Mg<2+>, Fe<3+> and F<-> co-doped composite lithium-rich anode 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 poor cycle stability, incomplete understanding of the mechanism of action, and fast capacity decay, and achieve improved cycle capacity retention ability, reduction of irreversible capacity loss, effect of low reversibility

Inactive Publication Date: 2013-05-01
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

5O 2 The cycle stability is not good, and the capacity decays quickly after multiple cycles. When the charge and discharge current increases, the capacity decays quickly
The mechanism of doping lithium ions on the electrochemical performance of materials is not yet fully understood

Method used

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  • Cr3&lt;+&gt;, Mg&lt;2+&gt;, Fe&lt;3+&gt; and F&lt;-&gt; co-doped composite lithium-rich anode material and preparation method thereof

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:Mg(NO 3 ) 2 ·6H 2 O:Fe(NO 3 ) 3 9H 2 O:Cr(NO 3 ) 3 9H 2 O: LiF is 1.091: 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 of 1.5 times of all metal ion total amounts, 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 130° 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 sheet, the...

Embodiment 2

[0014] Example 2: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 O:Mg(NO 3 ) 2 ·6H 2 O:Fe(NO 3 ) 3 9H 2 O:Cr(NO 3 ) 3 9H 2 O: LiF is 1.465: 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 the amount of all metal ions is 2.5 times fully stirs to Dissolve completely; raise the temperature of the system to 85°C and continue to stir until 85% of the water evaporates, then 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 5 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 calcined i...

Embodiment 3

[0015] Embodiment 3: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 O: MgCl 2 ·6H 2 O:Fe(NO 3 ) 3 9H 2 O:Cr(NO 3 ) 3 9H 2 O: LiF is 1.168: 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 2.0 times fully stirs to Dissolve completely; raise the temperature of the system to 78°C and continue to stir until 78% 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 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 temper...

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Abstract

The invention discloses a Cr3<+>, Mg<2+>, Fe<3+> and F<-> co-doped layer-layer composite lithium-rich anode material xLi2MnO3.(1-x)LiMn0.5Ni0.5O2(x is not less than 0 and not more than 0.5). The Cr3<+>, Mg<2+>, Fe<3+> and F<-> co-doped layer-layer composite lithium-rich anode material is characterized in that a stoichiometric equation of the anode material is xLi2MnO3.(1-x)Li1+n-y(Mn0.5Ni0.5)1-m-n-pCrmMgnFepO2-yFy, wherein x is not less than 0 and not more than 0.5, m is not less than 0.01 and not more than 0.05, n is not less than 0.01 and not more than 0.05, p is not less than 0.01 and not more than 0.05 and y is not less than 0.01 and not more than 0.06. The preparation method comprises the following steps: adding soluble lithium compound, soluble manganese salt, soluble nickel salt, soluble magnesium salt, soluble chromium salt, soluble iron salt and lithium fluoride into deionized water according to the stoichiometric ratio of the molecular formula; adding tartaric acid of which the mol ratio is 1.5-2.5 times of the total amount of metal ions and uniformly and fully stirring until the mixture is dissolved; and condensing, gelating, drying, grinding, decomposing, tabletting and calcining the solution to obtain the Cr3<+>, Mg<2+>, Fe<3+> and F<-> co-doped layer-layer composite lithium-rich anode material. The prepared anode material has excellent circulation capacity holding capacity and magnification characteristic.

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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IPC IPC(8): H01M4/505H01M4/525
CPCY02E60/122Y02E60/10
Inventor 冯琳水淼程亮亮杨天赐舒杰任元龙郑卫东高珊徐晓萍
Owner NINGBO UNIV
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