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Surface-coated solid solution cathode material and preparation method thereof

A positive electrode material and surface coating technology, which is applied in the field of lithium-ion battery solid solution positive electrode materials and its preparation, can solve the problems of poor rate performance, low first Coulombic efficiency, poor rate performance improvement, etc.

Active Publication Date: 2015-11-04
JIANGSU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, lithium-rich manganese-based layered solid solution cathode materials also have some fatal defects, such as low initial Coulombic efficiency, poor rate performance, etc. These defects seriously affect the application of solid solution cathode materials; for these defects, researchers have adopted many methods To carry out research and improvement, the most commonly used method is surface coating, such as coating metal oxide (Al 2 o 3 , MnO 2 , MgO, VO 2 ,TiO 2 ), fluoride (AlF 3 ), carbon and other ionic conductors (LiCoPO 4 , LiNiPO 4 , Li 4 Ti 5 o 12 , Li 3 VO 4 , LiAlO 2 , LiN 0.5 mn 1.5 o 4 ); after metal oxide coating, although the first Coulombic efficiency can be improved, the improvement of the rate performance is not good. limited; therefore, it is necessary to develop new methods for surface coating modification of lithium-rich manganese-based solid solution cathode materials

Method used

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  • Surface-coated solid solution cathode material and preparation method thereof
  • Surface-coated solid solution cathode material and preparation method thereof
  • Surface-coated solid solution cathode material and preparation method thereof

Examples

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Embodiment 1

[0019] Example 1: Weigh nickel sulfate, cobalt sulfate, manganese sulfate and NaOH according to the stoichiometric ratio, and prepare a 0.1mol / L solution, and control the temperature of the aqueous solution at 50°C and the pH value at 7.0 by ultrasonic external field assisted coprecipitation method , to prepare the precursor; then mixed with lithium carbonate weighed according to the stoichiometric ratio, mechanically activated for 1h, calcined at 400°C for 1h, then calcined at 750°C for 8h, and finally cooled to obtain a lithium-rich solid solution positive electrode material 0.5Li 2 MnO 3 0.5LiNi 0.3 co 0.4 mn 0.3 o 2 ; Then follow Li 0.5 Ni 0.5 mn 1.5 o 4 The stoichiometric ratio of lithium acetate, manganese acetate and nickel acetate was weighed, oxalic acid was selected as the organic chelating agent, they were dissolved in an aqueous solution, and stirred into a sol at 50 ° C, and an appropriate proportion of lithium-rich solid solution positive electrode materia...

Embodiment 2

[0020] Example 2: Weigh nickel nitrate, cobalt nitrate, manganese nitrate and NaOH according to the stoichiometric ratio, and prepare a 0.5mol / L solution, and control the temperature of the aqueous solution at 60°C and the pH value at 9.0 by ultrasonic external field assisted coprecipitation method , to prepare the precursor; then mixed with lithium carbonate weighed according to the stoichiometric ratio, mechanically activated for 12 hours, calcined at 450°C for 12h, then calcined at 850°C for 24h, and finally cooled to obtain a lithium-rich solid solution positive electrode material 0.5Li 2 MnO 3 0.5LiNi 0.5 mn 0.5 o 2 ; Then follow Li 0.35 Cr 0.5 mn 1.5 o 4 The stoichiometric ratio of lithium acetate, manganese acetate and chromium acetate was weighed, oxalic acid was selected as the organic chelating agent, they were dissolved in aqueous solution, and stirred into a sol at 60 ° C, and an appropriate proportion of lithium-rich solid solution positive electrode materia...

Embodiment 3

[0021] Embodiment 3: Weigh nickel sulfate, cobalt sulfate, manganese sulfate and NaOH according to the stoichiometric ratio, and prepare a 1mol / L solution, and control the temperature of the aqueous solution at 80°C and the pH value at 11.0 by ultrasonic external field assisted coprecipitation method, Prepare the precursor; then mix it with lithium carbonate weighed according to the stoichiometric ratio, mechanically activate it for 6 hours, bake it at 400°C for 6 hours, then bake it at 900°C for 12 hours, and finally cool it to obtain a lithium-rich solid solution positive electrode material 0.5Li 2 MnO 3 0.5LiNi 0.4 co 0.4 mn 0.2 o 2 ; Then follow Li 0.7 Ti 0.5 mn 1.5 o 4 The stoichiometric ratio of lithium acetate, manganese acetate and Ti(C 4 h 9 O) 4 , choose ethylene glycol as the organic chelating agent, dissolve them in the aqueous solution, and stir them into a sol at 70 ° C, and put an appropriate proportion of lithium-rich solid solution positive electrode...

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Abstract

The invention relates to a surface-coated solid solution cathode material and a preparation method thereof and belongs to the field of new energy material. The surface-coated solid solution cathode material of the invention is obtained by coating the surface of (x)Li2MnO3.(1-x)LiNiCoMn<1-a-b>O2 with Li<z>A<0.5>Mn<1.5>O<y>, and the coating amount accounts for 1 to 20 percent of the total mass of the cathode material. The material takes full use of Li2O deintercalated in the charging process of lithium-rich solid solution cathode material, and the Li2O is further intercalated in Li<z>A<0.5>Mn<1.5>O<y> to form the spinel-type surface coating LiA<0.5>Mn<1.5>O4 with three-dimensional ion diffusion channels. The transmission of the lithium-ions in the surface of the (x)Li2MnO3.(1-x)LiNiCoMn<1-a-b>O2 cathode material is effectively improved so as to improve first coulombic efficiency and rate capability of the surface-coated sosoloid cathode material.

Description

Technical field [0001] The invention involves a lithium -ion battery solid soluble positive material and its preparation method, which belongs to the field of new energy materials. Background technique [0002] Lithium -rich manganese grass -layer solid -soluble orthopedic material XLI 2 MNO 3 · 1-xlimo 2 (0 <x <1, m = ni, co, mn) Due to a high discharge ratio (> 250mAhg -1 ), Higher energy density and excellent circulating performance, and are hoped to become the first choice of positive electrode materials for the new generation of lithium -ion power batteries. [0003] However, there are some fatal defects for lithium -enriched lithium manganese -level solid -soluble orthopedic materials, such as low efficiency and poor percentage performance of the first Kuron, which seriously affects the application of solid -soluble positive materials; for these defects, researchers have adopted many methods.Research and improvement. At present, more methods are surface covering, s...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M4/485
CPCH01M4/366H01M4/485H01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 刘云建王起亮杨广林李成浩张志强苏明如窦爱春潘凌理
Owner JIANGSU UNIV
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