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Method for modifying surface of anode material for lithium ion battery

A lithium-ion battery and positive electrode material technology, applied in the field of lithium-ion batteries and electrochemistry, can solve the problems of low initial efficiency, poor rate performance and cycle stability, etc., achieve convenient operation, improve initial charge and discharge efficiency, and have obvious effects Effect

Inactive Publication Date: 2013-05-08
SHANGHAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In order to solve the shortcomings of the material such as low efficiency for the first time, poor rate performance and cycle stability, a new method using AlF 3 A method of coating and modifying the surface of the material to improve the electrochemical performance of this type of material

Method used

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  • Method for modifying surface of anode material for lithium ion battery
  • Method for modifying surface of anode material for lithium ion battery
  • Method for modifying surface of anode material for lithium ion battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Weigh 0.1786g of Al(NO 3 ) 3 9H 2 O and 0.0529 g of NH 4 F, add 10ml deionized water respectively, stir for 1h to dissolve completely. Utilize the NaOH solution that mass concentration is 5% to adjust pH of aluminum nitrate solution to be 8, then weigh 2.5g Li 1.2 Ni 0.13 co 0.13 mn 0.54 o 2 , was added to the aluminum nitrate solution, stirred for 0.5h to obtain a uniform mixture, and then the ammonium fluoride solution was slowly added dropwise to the above mixture, and continued to stir for 10h. The product was collected, then suction filtered and washed three times, and the sample was placed in a vacuum drying oven at 80°C overnight. Finally, the material was sintered in high-purity argon at 400 degrees for 10 hours to obtain AlF 3 Surface coated with modified Li 1.2 Ni 0.13 co 0.13 mn 0.54 o 2 .

[0024] The X-ray diffraction patterns of materials before and after coating are shown in figure 1 As shown, it can be seen from the figure that AlF 3 coa...

Embodiment 2

[0026] Adopt the same method as embodiment 1 to prepare AlF 3 Surface-modified cathode materials, the difference is the synthesis of AlF 3 The material is Al 2 (SO 4 ) 3 and NaF, the alkali solution to adjust the pH value is ammonia water, the final pH is 6, and the positive electrode material added is Li 1.19 Ni 0.16 co 0.08 mn 0.57 o 2 , using freeze-drying, and finally sintering at 700°C for 1h in high-purity nitrogen.

[0027] After the obtained coating material is assembled into a battery, the first charge and discharge curves at different rates are shown in image 3As shown, the first discharge specific capacities at 0.1C, 0.5C and 1C rates are 240.3, 204.2 and 182 mAh / g, respectively. Figure 4 is the cycle performance graph, the capacity retention rates of the materials before and after coating are 93.95% and 97.56% after 50 cycles at 1C rate.

Embodiment 3

[0029] Adopt the same method as embodiment 1 to prepare AlF 3 Surface-modified cathode materials, the difference is the synthesis of AlF 3 The material is Al(NO 3 ) 3 and KF, the alkali solution to adjust the pH value is potassium hydroxide, the final pH is 11, and the anode material added is LiNi 1 / 3 co 1 / 3 mn 1 / 3 o 2 , Stirred for 2h to collect the product. The sample was not washed, and the drying method was stirring and drying in a water bath, and finally sintered at 500 ° C for 8 h in high-purity helium.

[0030] Figure 5 is a scanning electron micrograph of the material before and after coating, where a is the sample before coating, and b is the sample after coating. It can be seen from the figure that the surface of the material after coating modification becomes denser and smoother, which is due to the coating of a layer of AlF on the surface of the material. 3 due to.

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Abstract

The invention relates to an anode material Li1+xM1-xO2 (M can be one or more of Ni, Co, Mn and Al, and x is not less than 0 and is not more than 1 / 3) for a lithium ion battery and a method for modifying the anode material of the lithium ion battery by coating AlF3 on the surface. The method comprises the steps of: firstly, weighing an aluminum source and a fluorine source (the coating quantity of AlF3 is equivalent to 0.5-10 percent by mass of the anode material) according to the stoichiometric ratio, and respectively adding water for dissolving; then adding a certain amount of alkali liquor in a stirred aluminum source solution, regulating the pH value to be 4-11, adding an anode material to be coated, continuously stirring for 0.5-10hours, and then adding a fluorine salt; and drying and then sintering a precursor in an inert gas for 1-10hours at a temperature of 200-700 DEG C to obtain the AlF3 surface coating modified anode material. According to the invention, the first-time charge and discharge efficiency, rate discharge and circulatory stability of the anode material can be improved; and the method has the advantages of simple process, low cost and convenience in operation, and is suitable for industrialized production.

Description

technical field [0001] The invention relates to a lithium-ion battery cathode material and a method for surface modification thereof, belonging to the field of lithium-ion batteries and electrochemistry. Background technique [0002] Lithium-ion batteries have been widely used in various portable electronic devices, and have broad application prospects in the fields of electric vehicles and energy storage batteries in the future. This puts forward higher requirements on the performance of lithium-ion battery cathode materials. In recent years, layered transition metal oxide cathode materials Li 1+x m 1-x o 2 (M can be one or more of Ni, Co, Mn, Al, 0≤x≤1 / 3), such as LiCoO 2 , LiMn 2 o 4 , LiNi 0.5 mn 0.5 o 2 , LiNi 0.8 co 0.15 al 0.05 o 2 , LiNi 1 / 3 co 1 / 3 mn 1 / 3 o 2 , Li 1.1 al 0.05 mn 1.85 o 4 have received extensive attention from researchers. When the charge voltage is greater than 4.6V, the discharge specific capacity of this material can exceed 25...

Claims

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Application Information

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IPC IPC(8): H01M4/505H01M4/525H01M4/62H01M4/131H01M4/1391
CPCY02E60/122Y02E60/10
Inventor 蒋永赵兵庄华蔡新辉马启亮焦正苏玲刘瑞喆
Owner SHANGHAI UNIV
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