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A kind of modification method of ternary cathode material

A positive electrode material and modification technology, which is applied in the direction of electrical components, battery electrodes, circuits, etc., can solve problems such as cycle performance deterioration, rate performance impact, surface layer structure collapse, etc., achieve good cycle performance, reduce battery bulging, reduce The effect of pH

Active Publication Date: 2015-11-11
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although the lithium-nickel-cobalt-manganese composite oxide ternary cathode material has many advantages mentioned above, due to its Ni 2+ with Li + The ionic radius is relatively close, and it is easy to appear Ni 2+ with Li + The mixing phenomenon makes the material prone to lithium precipitation in the air, and forms Li on the surface of the ternary material. 2 CO 3 Lithium compounds such as LiOH make the PH value of the ternary material higher, resulting in poor electrochemical performance of the material
If the pH value is too high, on the one hand, it is not conducive to the dispersion and stirring of the slurry; on the other hand, the material with a too high pH value will chemically react with the aluminum foil to form Al(OH) 3 , producing flocculent precipitates, for Li + At the same time, the released gas will cause the battery to bulge during the charging and discharging process, especially at high temperature, which will have a serious impact on the capacity, cycle life, and rate performance of the battery. influences
At present, the traditional coating generally adopts the solid phase coating method, and the coating cannot be uniformly coated on the surface of the material, resulting in the erosion of fluoride and transition metals on the surface of some positive active particles of the material during the charge and discharge process. The dissolution of ions causes the surface layered structure to collapse and cycle performance to deteriorate

Method used

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  • A kind of modification method of ternary cathode material
  • A kind of modification method of ternary cathode material
  • A kind of modification method of ternary cathode material

Examples

Experimental program
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Effect test

Embodiment 1

[0025] Will LiNi 1 / 3 co 1 / 3 mn 1 / 3 o 2 Weigh 100g and add it into 100ml of 0.05mol / L acetic acid solution, stir magnetically for 30min, and dry after washing. Add 0.59g of lanthanum oxide to the dried material, the mass of the lanthanum element is 0.5% of the mass of the ternary positive electrode material, then add an appropriate amount of distilled water, stir evenly, form a slurry, and put it into a sagger. Sinter directly at 600° C. for 4 hours in an air atmosphere, cool to room temperature, and grind through a 400-mesh sieve to obtain a lanthanum oxide-coated ternary cathode material.

[0026] The lanthanum oxide-coated LiNi prepared in this example 1 / 3 co 1 / 3 mn 1 / 3 o 2 , using a metal lithium sheet as the counter electrode, and assembled into a CR2032 button battery in a glove box. The charge and discharge voltage range is 3.0~4.4V. Under the charge and discharge rate of 0.1C, the first charge and discharge capacity of the fabricated battery reaches 193mAh / g and...

Embodiment 2

[0028] Will LiNi 0.5 co 0.2 mn 0.3 o 2 Weigh 100g and add it into 100ml of 0.08mol / L acetic acid solution, stir magnetically for 30min, and dry after washing. Add 2.17g of lanthanum carbonate octahydrate to the dried material, the mass of the lanthanum element is 1.0% of the mass of the ternary positive electrode material, then add an appropriate amount of distilled water, stir evenly, form a slurry, and put it into a sagger. Sinter directly at 900° C. for 6 hours in an air atmosphere, cool to room temperature, and grind through a 400-mesh sieve to obtain a lanthanum oxide-coated ternary positive electrode material.

[0029] The lanthanum oxide-coated LiNi prepared in this example 0.5 co 0.2 mn 0.3 o 2 The positive electrode material was assembled into a battery. The specific method was the same as in Example 1. Under the charge and discharge rate of 0.1C, the first charge and discharge capacity reached 205mAh / g and 184mAh / g, and the first charge and discharge efficienc...

Embodiment 3

[0031] Will LiNi 0.5 co 0.2 mn 0.3 o 2 Weigh 100g and add it into 100ml of 0.11mol / L acetic acid solution, stir magnetically for 30min, and dry after washing. Add 2.65g of lanthanum chloride to the dried material, the mass of the lanthanum element is 1.5% of the mass of the ternary positive electrode material, then add an appropriate amount of distilled water, stir evenly, form a slurry, and put it into a sagger. Sinter directly at 800° C. for 7 hours in an air atmosphere, cool to room temperature, and grind through a 400-mesh sieve to obtain a lanthanum oxide-coated ternary cathode material.

[0032] The lanthanum oxide-coated LiNi prepared in this example 0.5 co 0.2 mn 0.3 o 2 The positive electrode material was assembled into a battery. The specific method was the same as in Example 1. Under the charge and discharge rate of 0.1C, the first charge and discharge capacity reached 206mAh / g and 181mAh / g, and the first charge and discharge efficiency was 88%. After 50 cycl...

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Abstract

The invention discloses a modifying method of a ternary anode material. The modifying method is characterized by comprising the following steps: (1), adding the ternary anode material LiNixCoyMnzO2 into an acetic acid solution, stirring for 20 min-40 min, and then washing and drying, wherein x is not less than 0.3 and not more than 1, y is not less than 0 and not more than 0.5, z is not less than 0 and not more than 0.5, and (x+y+z) is equal to 1; (2), adding a lanthanum element into the dried ternary anode material, wherein the lanthanum element is metal lanthanum or a compound of metal lanthanum of which the mass is 0.5%-2% of the mass of the ternary anode material; then adding distilled water, uniformly stirring to form slurry; and (3), directly heating the slurry material in an air atmosphere to 600-900 DEG C according to a heating rate step by step, sintering for 2-8 hours, cooling to the room temperature, grinding and sieving to obtain the lanthanum oxide-coated ternary anode material.

Description

technical field [0001] The invention relates to the technical field of lithium ion batteries, in particular to a method for modifying a ternary positive electrode material. Background technique [0002] Due to the advantages of small size, light weight, long cycle life, large specific energy and no memory effect, lithium-ion batteries have been widely used in portable electronic products and new energy vehicles. The positive electrode material is one of the core parts of lithium-ion batteries. , which greatly affects the performance of lithium-ion batteries. [0003] At present, among the cathode materials of lithium-ion batteries, the most studied is LiCoO 2 , LiNiO 2 and LiMn 2 o 4 . LiCoO 2 It is the earliest lithium-ion battery cathode material to realize industrialization and commercial application, but cobalt is a rare resource, expensive, and has certain pollution to the environment; LiNiO 2 Although the theoretical specific capacity is high, the synthesis is d...

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 夏继平叶学海刘红光陈威张晓波于晓薇卢阳
Owner CNOOC TIANJIN CHEM RES & DESIGN INST