Lithium cobaltate composite oxide coated by hydrolytic precipitation-roasting method and manufacturing method thereof

A technology for coating lithium cobaltate and composite oxides, which is applied in the field of new energy material preparation, can solve the problems of failure to meet the requirements of commercial applications, complicated operation process, and inability to use, so as to improve cycle stability and anti-overshooting. The effect of charging performance

Inactive Publication Date: 2010-10-27
北京圣比和科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these findings are of great importance to LiCoO 2 There are some improvements in cycle performance or/and anti-overcharge performance, but none of them meet the requirements of commercial applications
However, Chinese Patent CN1697212A, Japanese Patent Laid-Open 2001-243948 and U.S. Patent US6555269B2 use Mg, Ti, Si, etc. to coat LiCoO 2 , improved LiCoO 2 Excellent high temperature performance and anti-overcharge performance, however, this coating method uses the sol-gel method, using organic solvents and organic salts as the main raw materials, which cannot be economically used in industrial producti

Method used

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  • Lithium cobaltate composite oxide coated by hydrolytic precipitation-roasting method and manufacturing method thereof
  • Lithium cobaltate composite oxide coated by hydrolytic precipitation-roasting method and manufacturing method thereof
  • Lithium cobaltate composite oxide coated by hydrolytic precipitation-roasting method and manufacturing method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Zr 4+ The preparation of solution: 177.7g Zr(SO 4 ) 2 4H 2 O was dissolved in 500mL of pure water, and the resulting aqueous solution was diluted to 1000mL to prepare 0.5mol / L Zr 4+ solution.

[0035] Weigh 20kg CoCO 3 (particle size D 50 2μm) and 6.99kg LiOH·H 2 O (particle size D 50 2μm), the Li / Co (molar ratio) of the ingredients is 0.99, after mixing thoroughly by dry method. The mixture was first fired at 600°C for 8 hours and then at 1100°C for 3 hours. Pulverize and classify the synthesized product to obtain LiCoO to be coated 2 . XRD analysis showed that the LiCoO 2 With standard α-NaFeO 2 Layered structure. The measured tap density is 2.55g / cm 3 , BET specific surface area is 0.43m 2 / g, particle size D 50 is 7.2 μm.

[0036] Get the above prepared 0.5mol / L Zr 4+ Put 10.2mL of the solution in a 2L reactor with a stirring device, add water to dilute to 1000mL, take 1000g of the LiCoO prepared above 2 Add it into the reactor, stir for 5 minutes...

Embodiment 2

[0046] Get the prepared Zr of embodiment 1 4+ Put 1021.5mL aqueous solution in a 2L reactor with stirring device, add pure water to dilute to 1000mL, take 1000g of LiCoO to be coated prepared in Example 1 2 Add it into the reactor, stir for 5 minutes, adjust the pH value to 10.0 with 10% (wt.) NaOH solution, and filter.

[0047] The precursor obtained by the above filtration was calcined at 1000 °C for 3 hours to obtain the coated LiCoO 2 composite oxides.

[0048] Analysis showed that the coating layer on the surface of the product particles had a thickness of about 35nm. Other physical properties of the product are listed in Table 1. According to the method of Example 1, the electrical performance indicators of the product when it is a positive electrode active material are listed in Table 2.

Embodiment 3

[0050] Ti 4+ Solution preparation: 120.0g Ti(SO 4 ) 2 Dissolve in 500mL of 5% (wt.) dilute sulfuric acid solution, dilute the resulting aqueous solution to 1000mL, and prepare 0.5mol / L Ti 4+ solution.

[0051] Take the Ti prepared above 4+ 10.2 mL of the solution was placed in a 2L reactor with a stirring device, diluted to 1000 mL with pure water, and 1000 g of the LiCoO to be coated prepared in Example 1 was taken. 2 Add it into the reactor, stir for 5 minutes, adjust the pH value to 8.0 with 10% (wt.) NaOH solution, and filter.

[0052] The precursor obtained by the above filtration was calcined at 650 °C for 20 hours to obtain titanium-coated LiCoO 2 composite oxides.

[0053] XRD analysis shows that the product has standard α-NaFeO 2 Layered structure. X-ray photoelectron spectroscopy comprehensive analysis shows that after the above method, in LiCoO 2 A layer of LiCo with a thickness of about 15 nm is formed on the particle surface 1-y Ti y o 2(0

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Abstract

The invention provides a lithium cobaltate composite oxide coated by a hydrolytic precipitation-roasting method. When being used as an anode material of a lithium ion battery, the lithium cobaltate composite oxide can enable the performance of the lithium ion battery, especially cycle performance and overcharge resistance to be excellent. The invention is characterized in that a manufacturing method comprises the following steps: adjusting the pH value of a water solution containing metallic ions to be coated by using a liquid phase hydrolytic precipitation method to obtain a coating precursor; roasting at high temperature; and using metal oxides (the metal is at least one of Ti or Zr) to coat the particle surface of lithium cobaltate which is represented by the general formula of Li1+xCoO2-a (x is greater than or equal to -0.1 and less than or equal to 0.1, and a is greater than or equal to -0.1 and less than or equal to 0.1).

Description

technical field [0001] The invention relates to a lithium cobalt oxide composite oxide coated by a hydrolysis precipitation-roasting method used as a positive electrode material of a lithium ion battery and a manufacturing method thereof, belonging to the technical field of new energy material preparation. Background technique [0002] Lithium cobalt oxide (LiCoO 2 ) compounds have stable electrochemical properties, high specific capacity and specific energy density, and are easy to synthesize. They are currently widely used cathode materials for commercial lithium-ion batteries. [0003] LiCoO 2 The theoretical specific capacity is 274mAh / g. During the charging process of the battery, although almost all lithium ions can theoretically be released by electrochemical routes, only about 0.5mol Li + Capable of reversible de-intercalation, a small amount of overcharging will reduce the thermal stability and cycle performance of the material. With Li x CoO 2 Lithium-ion bat...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/48H01M4/52H01M4/58H01M4/04H01M4/02
CPCY02E60/10
Inventor 叶尚云张平伟李锡力
Owner 北京圣比和科技有限公司
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