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Ni2+, 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: 2016-07-06
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the current surface modification components usually only protect the surface structure of the electrode active material, and have limited effects on improving the rate characteristics.
[0007] Moreover, since the volume of the electrode material changes periodically during the cycle, it is inevitable that the electrode material and the coating layer will be detached after a long-term cycle, resulting in the loss of the coating layer.

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=1.1:0.55:0.45 (molar ratio), mix evenly, dissolve in deionized water, add tartaric acid 1.2 times the total amount of all metal ions and stir well until it is completely dissolved; increase the temperature of the system to 70 Continue stirring at °C until 71% of the water has evaporated, at which 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 in a tube furnace at a rate of 2°C / min to 500°C and calcined at this temperature for 3 hours. After cooling, the powder was taken out, and the powder was pulverized in a mortar for 10 minutes. The powder was pressed with a pressure of 100MPa After being formed into a sheet, the temperature is raised to 850°C for 5 hours at a rate of 2°C / min in a tube furnace, and the lithium-rich cathode material is obtained af...

Embodiment 2

[0014] Example 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 tartaric acid is added in the amount of 1.6 times the total amount of all metal ions, and fully stirred until it is completely dissolved; the temperature of the system is increased to 80 Continue stirring at °C until 75% of the water has evaporated, at which time the solution gradually becomes viscous and forms 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 in a tube furnace at a rate of 5°C / min to 550°C and calcined at this temperature for 4 hours. After cooling, the powder was taken out and pulverized in a mortar for 20 minutes. The powder was pressed with a pressure of 200MPa After the pellets are formed, the temperature is raised to 900°C for 5 hours at a rate of 5°C / min in a tube furnace, and the lithium-ri...

Embodiment 3

[0015] Example 3: LiNO 3 : Mn(CH 3 COO) 2 ·4H 2 O: Ni(CH 3 COO) 2 ·4H 2 O=1.2:0.6:0.4 (molar ratio), mix evenly, dissolve in deionized water, add tartaric acid 2.0 times the total amount of all metal ions and stir well until it is completely dissolved; increase the temperature of the system to 85 Continue stirring at °C until 83% of the water has evaporated, at which time the solution gradually becomes viscous and forms a jelly. The jelly-like substance 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 in a tube furnace at a rate of 10°C / min to 600°C and calcined at this temperature for 5 hours. After cooling, the powder was taken out, and the powder was pulverized in a mortar for 30 minutes. The powder was pressed with a pressure of 300MPa After the pellets were formed, the temperature was raised to 950°C at a rate of 9°C / min in a tube furnace and calcined for 15 hours, and the lithium-rich cathode material wa...

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Abstract

The invention relates to a Ni<2+>, Si<4+>, Zn<2+> and F<->-doped surface-modified lithium-enriched layer-layer composite anode material for solid electrolyte LiTi2PO4)x. A surface-modified layer of the layer-layer composite anode material has the stoichiometric formula of Li1+2x+2m+z-yZnxNimSizTi2-x-mP3-zO12-yFy, wherein x ranges from 0.1 to 0.5, y ranges from 0.1 to 0.2, ranges from 0.1 to 0.3 and z ranges from 0.1 to 0.3. The layer-layer composite anode material has the stoichiometric formula of xLi2MnO3.(1-x)LiMn0.5Ni0.5O2, wherein x is not less than 0 and not more than 0.5. The amount of substances of the surface-modified layer is 1-10% of that of the layer-layer composite anode material. The Ni<2+>, Si<4+>, Zn<2+> and F<->-doped surface-modified lithium-enriched layer-layer composite anode material has the characteristics of high cycle capacity retainability and excellent magnification.

Description

Technical field [0001] The invention relates to the manufacturing field of a lithium ion battery cathode material. Background technique [0002] Lithium-ion batteries have absolute advantages such as volume, high weight-to-energy ratio, high voltage, low self-discharge rate, no memory effect, long cycle life, and high power density. They have more than 30 billion US dollars / year share in the global mobile power market and far exceed others. The market share of batteries is the most promising chemical power source [Wu Yuping, Wan Chunrong, Jiang Changyin, Lithium Ion Secondary Battery, Beijing: Chemical Industry Press, 2002.]. However, since the commercialization of lithium-ion batteries in 1991, the actual specific capacity of cathode materials has been hovering between 100-180mAh / g. The low specific capacity of cathode materials has become a bottleneck in increasing the specific energy of lithium-ion batteries. If you want to effectively increase the energy density of lithium-i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/48H01M4/505H01M4/62
CPCY02E60/10
Inventor 水淼杨天赐舒杰程亮亮冯琳任元龙郑卫东高珊
Owner NINGBO UNIV
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