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Ni2+, mn4+, si4+, zn2+, f-doped surface modified lithium-rich cathode material and preparation method

A lithium-rich cathode material and surface modification technology, applied in battery electrodes, electrical components, circuits, etc., can solve the problems of loss of coating layer effect and limited rate characteristic effect, and achieve low lithium ion conductivity and good cycle. Capacity retention and rate characteristics, drop-off reduction effect

Inactive Publication Date: 2016-05-18
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the current surface modification components usually only protect the surface structure of the electrode active material, and have limited effect on improving its rate characteristics. Moreover, because the electrode material will periodically change in volume during the cycle, the electrode material After a long-term cycle, there will inevitably be a detachment phenomenon between the coating layer and the coating layer, resulting in the loss of the coating layer

Method used

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  • Ni2+, mn4+, si4+, zn2+, f-doped surface modified lithium-rich cathode material and preparation method

Examples

Experimental program
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Effect test

Embodiment 1

[0013] Example 1: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2The ratio of O=1.1: 0.55: 0.45 (molar ratio) is uniformly mixed, dissolved in deionized water, and the amount of added substance is tartaric acid which is 1.2 times of the total amount of all metal ions and fully stirred until completely dissolved; the temperature of the system is raised to 70 °C Stirring was continued until 71% of the water evaporated, at which point the solution gradually became viscous and formed 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 temperature was raised to 850° C. for 5 hours in a tube furnace ...

Embodiment 2

[0014] Embodiment 2:: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 The ratio of O=1.5: 0.75: 0.25 (molar ratio) is evenly mixed, dissolved in deionized water, and the amount of the added substance is fully stirred until completely dissolved until the tartaric acid which is 1.6 times of the total amount of all metal ions is dissolved; the temperature of the system is raised to 80 °C Stirring was continued until 75% of the water evaporated, at which point the solution gradually became viscous and formed a jelly. The jelly-like substance was dried in an oven at 150° C. for 40 hours and then ground in a mortar for 20 minutes. The obtained powder was heated up to 550°C at a rate of 5°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. Form into a sheet, then heat up to 900° C. for 5 hours in a tube furnace at ...

Embodiment 3

[0015] Embodiment 3: LiNO 3 :Mn(CH 3 COO) 2 4H 2 O:Ni(CH 3 COO) 2 4H 2 The ratio of O=1.2: 0.6: 0.4 (molar ratio) is uniformly mixed, dissolved in deionized water, and the amount of added substance is tartaric acid 2.0 times of the total amount of all metal ions, fully stirred until completely dissolved; the temperature of the system is raised to 85 °C Stirring was continued until 83% of the water evaporated, at which point the solution gradually became viscous and formed 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 in a tube furnace at a rate of 9°C / min to 950°C for 15 hours, and the...

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Abstract

The invention discloses a Na5icon solid electrolyte LiTi2 (PO4)3 surface modified layer-layer composite lithium-rich positive pole material doped with Ni2+, Mn4+, Si4+, Zn2+ and F-. The stoichiometric equation of a surface modified layer is Li1+2x+m+z-yZnx (Mn0.5Ni0.5)mSizTi2-x-mP3-zO12-yFy, wherein x=0.1-0.5; y=0.1-0.2; m=0.1-0.3; and z=0.1-0.3. The stoichiometric equation of the layer-layer composite lithium-rich positive pole material is xLi2MnO3.(1-x)LiMn0.5Ni0.5O2, wherein x is more than or equal to 0 and is less than or equal to 0.5. A substance of the surface modified layer is 1%-10% of the positive pole material. The surface modified positive pole material has high circulation capacity holding capability and an excellent multiplying power 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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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/505H01M4/525
CPCY02E60/10
Inventor 杨天赐水淼舒杰程亮亮冯琳任元龙郑卫东高珊
Owner NINGBO UNIV
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