A solid phase synthesis al 3+ ,cu 2+ Doped cubic bismuth fluoride lithium ion battery positive electrode material and preparation method thereof

A lithium-ion battery and cubic structure technology, which is applied in battery electrodes, secondary batteries, structural parts, etc., can solve the problems that the electron transport characteristics are greatly affected, the process conditions are harsh, and the content of by-products is too high to be used as positive electrode materials. , to achieve the effect of improving capacity cycle stability, avoiding side reaction products, and excellent electrochemical performance

Active Publication Date: 2017-08-15
嘉兴市燕知网络科技有限公司
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  • Application Information

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Problems solved by technology

The conventional synthesis method of bismuth fluoride is to react with hydrogen fluoride gas and metal oxide / hydroxide or fluorine gas and metal element at high temperature. The process conditions are harsh, the equipment requirements are very high, and the energy consumption is high, so the price is very expensive.
However, the preparation of bismuth fluoride by liquid phase reaction is often unable to be used as a positive electrode material because the by-product content is too high, and it is also uneconomical due to the high cost of waste liquid.
Bismuth fluoride, as a cathode material for lithium-ion secondary batteries, also has a negative characteristic that its electronic conductivity is extremely low, so it will cause a high polarization voltage during charge and discharge.
[0007] In addition, the crystal form and morphology of bismuth fluoride have a great influence on the electron transport characteristics in the crystal lattice, so it is directly related to the electrochemical performance of lithium ion batteries such as charge and discharge speed, capacity and cycle capacity retention; ion doping is a It is an effective way to adjust the microstructure of the lattice and change the electron and ion transport characteristics of the lattice. However, the mechanism of ion doping or even multi-ion synergistic doping on the matrix is ​​very complicated, and the effect is often unpredictable.

Method used

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  • A solid phase synthesis al  <sup>3+</sup> ,cu  <sup>2+</sup> Doped cubic bismuth fluoride lithium ion battery positive electrode material and preparation method thereof
  • A solid phase synthesis al  <sup>3+</sup> ,cu  <sup>2+</sup> Doped cubic bismuth fluoride lithium ion battery positive electrode material and preparation method thereof

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Embodiment 1

[0021] Embodiment 1: the perfluorinated aluminum nitrate nonahydrate of bismuth nitrate pentahydrate, the amount of bismuth nitrate pentahydrate substance 0.5%, copper sulfate pentahydrate pentahydrate of bismuth nitrate pentahydrate substance amount 0.5%, the perfluoro Heptanoic acid is mixed and put into a ball mill, the mass ratio of the ball mill and the material is 20:1, and ball milled at a speed of 200 rpm for 10 hours, this material is called material I; tetra-n-butylammonium fluoride, tetra-n-butyl ammonium Tween-60 with 0.5% of ammonium butyl ammonium fluoride and absolute ethanol with 2% of tetra-n-butyl ammonium fluoride are mixed and put into a ball mill. The mass ratio of the ball mill to the material is 20:1. Speed ​​ball milling 10 hours, this material is called material II; Material I and material II are according to the ratio of the amount of bismuth salt in material I and the ratio of the amount of quaternary ammonium salt material in material II that is 1: 3...

Embodiment 2

[0022] Embodiment 2: 2, the 2-difluoro rings of bismuth chloride, bismuth chloride substance amount 1.0% aluminum chloride, bismuth chloride substance amount 1.0% copper nitrate trihydrate, bismuth chloride quality 1.0% Propylcarboxylic acid is put into ball mill after mixing, and the mass ratio of ball mill and material is 20: 1, with the speed ball milling of 300 rev / mins 15 hours, this material is called material I; Tetramethylammonium fluoride, tetramethylammonium 1.0% op-10 of the mass of ammonium fluoride and 3% absolute ethanol of the mass of tetramethylammonium fluoride are mixed and put into a ball mill. Ball milling 15 hours, this material is called material II; Material I and material II are according to the ratio of the amount of bismuth salt in material I and the ratio of the amount of quaternary ammonium salt material in material II that is 1: 3 and material I and material II The crystallization control agent methacrylic acid and neopentyl methacrylate block copo...

Embodiment 3

[0023] Embodiment 3: with bismuth chloride, bismuth chloride substance amount 2% aluminum sulfate octadecahydrate, bismuth chloride substance amount 1.8% copper acetate monohydrate, bismuth chloride quality 2% perfluoroglutaric acid Put into ball mill after mixing, the mass ratio of ball mill and material is 20: 1, ball mill with the speed of 390 revolutions / min for 20 hours, this material is called material I; Benzyl trimethyl ammonium fluoride, benzyl trimethyl 2% Span-80 of benzyltrimethylammonium fluoride quality and 4% dehydrated alcohol of benzyltrimethylammonium fluoride quality are mixed and put into a ball mill. The mass ratio of the ball mill and the material is 20:1, and the Speed ​​ball milling per minute for 19 hours, this material is called material II; Material I and material II are according to the ratio of the amount of bismuth salt in material I and the ratio of quaternary ammonium salt material in material II to be 1: 3 ratio Put the crystallization control ...

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Abstract

The invention provides an Al<3+> and Cu<2+> doped cubic-structure bismuth fluoride lithium ion battery positive electrode material based on solid phase synthesis and a preparation method thereof. According to the method, a quaternary ammonium salt utilizing fluorine as negative ions is adopted as a raw material so as to directly synthesize cubic-structure bismuth fluoride by virtue of a large-group steric hindrance effect and the effect of a specific accessory ingredient in a solid phase manner; furthermore, Cu<2+> is doped, so that the average discharge electric potential of the raw material is improved; Al<3+> is doped, so that the capacity circulation stability is improved; serving as a lithium ion battery positive electrode material, the bismuth fluoride material has a specific capacity greater than 200mAh.g<-1>. The method is low in equipment requirement and high in product purity, and can be used for avoiding the problem that byproducts such as multiple complex salts of bismuth fluoride are generated during solid-phase reaction; the product has excellent electrochemical performance.

Description

technical field [0001] The invention relates to the technical field of a method for manufacturing a high-capacity bismuth fluoride composite lithium battery cathode material. Background technique [0002] Lithium-ion secondary batteries have the absolute advantages of high volume, weight-to-energy ratio, high voltage, low self-discharge rate, no memory effect, long cycle life, and high power density. Currently, the global mobile power market has an annual share of more than 30 billion US dollars and Gradually grow at a rate of more than 10%. Especially in recent years, with the gradual depletion of fossil energy, new energy sources such as solar energy, wind energy, and biomass energy have gradually become alternatives to traditional energy sources. Among them, wind energy and solar energy are intermittent, and a large amount of energy is used simultaneously to meet the needs of continuous power supply. Energy storage batteries; urban air quality problems caused by automobi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/58H01M10/0525
CPCH01M4/582H01M10/0525Y02E60/10
Inventor 徐玲霞水淼徐晓萍陈超陈姝舒杰任元龙
Owner 嘉兴市燕知网络科技有限公司
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