Layered lithium-rich anode material clad by metal fluoride, and preparation method thereof

A technology of lithium-rich positive electrode materials and positive electrode materials, applied in battery electrodes, electrical components, circuits, etc., can solve the problems of large irreversible capacity and poor high rate performance, and achieve improved electrochemical performance, high specific capacity, and good rate performance Effect

Inactive Publication Date: 2012-06-13
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

From a practical point of view, the main problems existing in layered lithium-rich materials are:

Method used

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  • Layered lithium-rich anode material clad by metal fluoride, and preparation method thereof
  • Layered lithium-rich anode material clad by metal fluoride, and preparation method thereof
  • Layered lithium-rich anode material clad by metal fluoride, and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] 1) Lithium-rich cathode material Li[Li 0.22 Ni 0.17 mn 0.61 ]O 2 Preparation: with the acetate of Li, Ni and Mn as raw material, add excessive oxalic acid (excessive 10%), be mixed with 100 milliliters of metal ion total concentration and be the mixed aqueous solution of 0.5 mole per liter and transfer in the reactor, then Add 10 ml of glacial acetic acid, stir evenly and then seal it; place the reaction kettle in an oven at 120°C for 8 hours and then cool it down naturally, transfer the solution to a beaker and stir until the solvent is completely evaporated; grind the solid product into powder and transfer it to a crucible , baked at 450°C for 2 hours, and after cooling, the material was ground and pressed into tablets; the pressed material was placed in a muffle furnace and sintered at a high temperature of 750°C for 8 hours to obtain Li[Li 0.22 Ni 0.17 mn 0.61 ]O 2 .

[0024] 2) YF 3 Coated Li[Li 0.22 Ni 0.17 mn 0.61 ]O 2Preparation: Take 5 mmoles of Li[...

Embodiment 2

[0028] Change the yttrium nitrate hexahydrate into calcium nitrate tetrahydrate in step 2) in the embodiment 1, the mol ratio of Ca and F is 1: 2, other are the same as embodiment 1. Electrochemical performance tests such as image 3 As shown, at a current density of 300 mA / g, the coated CaF 2 The discharge specific capacity of the final material reaches up to 145 milliampere hours per gram, and the discharge specific capacity is obviously improved, and the cycle performance of the material is also improved.

Embodiment 3

[0030] Change the yttrium nitrate hexahydrate in step 2) in embodiment 1 to lanthanum nitrate hexahydrate, LaF 3 with Li[Li 0.22 Ni 0.17 mn 0.61 ]O 2 Ratio control is 3wt%, other is with embodiment 1. Figure 4 is material coated LaF 3 The discharge cycle curves at different current densities before and after, it can be seen from the figure that the rate performance of the coated material has been significantly improved.

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Abstract

The invention relates to a layered lithium-rich anode material clad by metal fluoride, and a preparation method thereof. According to the invention, a layered lithium-rich material Li[Li(1-2x)/3MxMn(2-x)/3]O2 is prepared with a combined technology of a oxalate precipitation method and a hydro-thermal method, wherein M is Ni, Co, Cr or any two of them which coexist, and x=0 to 0.33. The lithium-rich material is impregnated in a solution of soluble salts of metals such as yttrium, magnesium and iron; a soluble fluoride solution is added to the mixture, wherein n(Me):n(F)=1:y; the solution is continuously stirred for 3-8h in a water bath with a temperature of 60-90 DEG C; the solution is subject to centrifugal washing, and is dried under a temperature of 60 DEG C in a vacuum thermostat; a material obtained after drying is roasted for 4-8h under a temperature of 400 DEG C and under the protection of argon gas, such that Li[Li(1-2x)/3NixMn(2-x)/3]O2 clad by a fluoride MeFy is prepared. The electrode material provided by the invention is advantaged in high electrochemical capacity, good cyclical stability, excellent rate performance, and the like. The preparation process is simple, the cost is low, and the reproducibility is good.

Description

technical field [0001] The invention relates to a metal fluoride-coated layered lithium-rich cathode material and a preparation method thereof, in particular to a metal fluoride-coated layered lithium-rich cathode material Li[Li (1-2x) / 3 m x mn (2-x) / 3 ]O 2 method of preparation. Background technique [0002] High-energy and high-power lithium-ion batteries are an inevitable demand in the future market. The key is to develop cathode materials for lithium-ion batteries with high capacity and high rate performance. The current commercial lithium-ion battery cathode materials mainly include LiCoO 2 , LiNiO 2 , LiMn 2 o 4 、LiFePO 4 etc., the capacities of these materials are all below 200 mAh / g. In contrast, the layered Li-rich materials Li[Li (1-2x) / 3 m x mn (2-x) / 3 ]O 2 The theoretical specific capacity exceeds 300 mAh / g, and the reported actual discharge specific capacity is also higher than 200 mAh / g. In addition, the lithium-rich layered material is cheap, ha...

Claims

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Application Information

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IPC IPC(8): H01M4/62H01M4/48
CPCY02E60/12Y02E60/10
Inventor 高学平冯欣李国然叶世海
Owner NANKAI UNIV
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