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Preparing method of zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material

A technology for ion batteries and positive electrode materials, applied in battery electrodes, secondary batteries, electrochemical generators, etc., can solve the problems of unsatisfactory overall performance improvement, affecting high rate performance of materials, and poor rate performance of positive electrode materials. , to achieve the effects of easy control of reaction conditions, high production efficiency and low cost

Inactive Publication Date: 2016-07-20
UNIVERSITY OF CHINESE ACADEMY OF SCIENCES
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Problems solved by technology

[0003] 1) The first-cycle Coulombic efficiency of lithium-rich manganese-based layered oxide cathode materials is low;
[0004] 2) The rate performance of lithium-rich manganese-based layered oxide cathode materials is poor;
[0005] 3) The cycle stability of lithium-rich manganese-based layered oxide cathode materials is poor;
[0006] 4) Lithium-rich manganese-based layered oxide cathode materials have obvious voltage attenuation problems with the increase in the number of cycles
These methods can improve the rate and cycle stability to a certain extent, and some experimental results can also inhibit the voltage decay, but the overall performance improvement is not very satisfactory.
Moreover, the traditional oxide-coated materials have poor lithium ion conductivity, which will affect the high-rate performance of the material.

Method used

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  • Preparing method of zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material
  • Preparing method of zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material
  • Preparing method of zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material

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preparation example Construction

[0036] The preparation method of the lithium-zirconate-coated lithium-ion battery lithium-rich manganese-based layered oxide positive electrode material proposed by the present invention adopts two methods for preparation, the first one is coated by a hydrothermal method, which includes the following steps:

[0037] Step1: Preparation of oxalate precursor

[0038] Cobalt metal salt CoSO 4 (Co(NO 3 ) 2 or CoCl 2 Metal salt NiSO with nickel 4 (Ni(NO 3 ) 2 Metal salt with manganese MnSO 4 (Mn(NO 3 ) 2 or MnCl 2 ) is dissolved in 50mL of water according to the molar ratio of x:y:(1-x-y) (where x4 (Ni(NO 3 ) 2 or NiCl 2 ) with manganese metal salt MnSO 4 (Mn(NO 3 ) 2 or MnCl 2 ) according to the molar ratio of x:(2 / 3-x / 3) was dissolved in 50mL water (where x2 C 2 o 4 or Na 2 C 2 o 4 or H 2 C 2 o 4 or (NH4) 2 C 2 o 4 Solution 50mL, under magnetic stirring, add the above precipitant solution into the above metal ion mixed solution to produce a precipitate, ...

Embodiment 1

[0052] (1) Cobalt metal salt CoSO 4 Metal salt NiSO with nickel 4 Metal salt with manganese MnSO 4 Dissolve in 50mL water according to the molar ratio of 1.5:1.5:7, so that the total molar concentration of metal ions is 1mol / L, to obtain a mixed solution of metal ions; configure 50mL of K2C2O4 solution with a molar concentration of 1mol / L, and stir the above precipitate The solution was added to the above metal ion mixed solution to produce a precipitate. After stirring for 2 hours, centrifuge, wash the precipitate twice with deionized water and absolute ethanol respectively, and dry the precipitate in an oven at 80°C for 12 hours. Obtain the oxalate precursor, the molecular formula of the oxalate precursor is: Mn 7 Ni 1.5 co 1.5 C 2 o 4 2H 2 O;

[0053](2) Disperse the oxalate precursor obtained in the above step (1) in absolute ethanol at a mass ratio of 1:5, add 10 μL of ammonia water, stir and ultrasonically disperse for 10 minutes, according to Zr:Mn=7:100 Molar ...

Embodiment 2

[0056] (1) Cobalt metal salt CoSO 4 Metal salt NiSO with nickel 4 Metal salt with manganese MnSO 4 Dissolve in 50mL water according to the molar ratio of 1.0:1.0:8, so that the total molar concentration of metal ions is 2mol / L to obtain a mixed solution of metal ions; configure 50mL of K2C2O4 solution with a molar concentration of 2mol / L, and stir the above precipitate The solution was added to the above metal ion mixed solution to produce a precipitate. After stirring for 2 hours, centrifuge, wash the precipitate twice with deionized water and absolute ethanol respectively, and dry the precipitate in an oven at 80°C for 12 hours. Obtain the oxalate precursor, the molecular formula of the oxalate precursor is: Mn 8 Ni 1.0 co 1.0 C 2 o 4 2H 2 O;

[0057] (2) Disperse the oxalate precursor obtained in the above step (1) in absolute ethanol at a mass ratio of 1:15, add 40 μL of ammonia water, stir and ultrasonically disperse for 10 minutes, according to Zr:Mn=15:100 Mola...

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Abstract

The invention discloses a preparing method of a zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material.The method comprises the following steps of preparing an oxalate precursor, preparing an oxide cladding oxalate precursor and preparing the zirconic acid lithium cladding lithium-rich manganese base layer oxide anode material.The preparing method has the advantages that the rate performance and cyclic stability of the lithium-rich manganese base layer oxide anode material can be improved, and voltage attenuation of the lithium-rich manganese base layer oxide anode material can be inhibited; 2, the synthetic technology is simple, the production efficiency is high, and the method is suitable for large-scale production; 3, the raw material needed by reactant is easy to obtain, is free of toxicity and low in cost, the production process does not need to be protected specially, the reaction condition is easy to control, and the obtained product has the advantages of being large in yield, good in result repeatability and the like.

Description

technical field [0001] The invention relates to a preparation method of a lithium-zirconate-coated lithium-ion battery lithium-rich manganese-based layered oxide positive electrode material, which belongs to the technical field of new energy. Background technique [0002] Lithium-rich manganese-based layered oxide cathode materials have attracted great attention in recent years due to their excellent capacity (>250mAhg-1) and energy density (>1000whkg-1). Especially at the moment when traditional cathode materials are still unable to meet the requirements of popularization of electric vehicles, it is particularly important and urgent to develop new cathode materials with higher energy density. However, at present, lithium-rich manganese-based layered oxide cathode materials are only in the laboratory stage, and the main problems in the commercialization process are as follows: [0003] 1) The first-cycle Coulombic efficiency of lithium-rich manganese-based layered oxi...

Claims

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Application Information

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IPC IPC(8): H01M4/1391H01M10/0525
CPCH01M4/1391H01M10/0525Y02E60/10
Inventor 刘向峰张继成张恒胡中波
Owner UNIVERSITY OF CHINESE ACADEMY OF SCIENCES
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