A solid phase synthesis co 2+ ,cu 2+ Doped orthogonal structure bismuth fluoride lithium ion battery positive electrode material and preparation method thereof

A lithium-ion battery, solid-phase synthesis technology, applied in battery electrodes, non-aqueous electrolyte battery electrodes, secondary batteries, etc., can solve the problems of harsh process conditions, great influence of electronic transport characteristics, and low electronic conductivity, etc. Achieve the effect of avoiding side reaction products, excellent electrochemical performance, and high product purity

Active Publication Date: 2017-08-15
NINGBO UNIV
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  • Application Information

AI Technical Summary

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

Examples

Experimental program
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Effect test

Embodiment 1

[0021] Embodiment 1: Cobalt chloride hexahydrate of bismuth nitrate pentahydrate, 0.6% of bismuth nitrate pentahydrate substance, copper sulfate pentahydrate pentahydrate of 0.6% bismuth nitrate pentahydrate substance, 0.6% of bismuth nitrate pentahydrate mass After fluoheptanoic acid is mixed, put it into a ball mill, the mass ratio of the ball mill and the material is 20:1, ball mill for 11 hours at a speed of 210 rpm, and this material is called material I; tetra-n-butylammonium fluoride, tetra-n-butylammonium 0.6% Tween-60 of butylammonium fluoride quality, 2.2% dehydrated alcohol of tetra-n-butylammonium fluoride quality are mixed and put into ball mill, the mass ratio of ball mill and material is 20: 1, with 200 rpm Ball milling at a speed of 10 hours per minute, 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 ...

Embodiment 2

[0022] Embodiment 2: Cobalt oxalate tetrahydrate with 1% of bismuth chloride, bismuth chloride substance, copper nitrate trihydrate with 1.1% of bismuth chloride substance, 1.2% of bismuth chloride quality 2,2-difluoro Cyclopropanecarboxylic 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 16 hours, this material is called material I; Benzyltrimethylammonium fluoride, 1% op-10 of the mass of benzyltrimethylammonium fluoride and 3% absolute ethanol of the mass of benzyltrimethylammonium fluoride are mixed and put into a ball mill, and the mass ratio of the ball mill to the material is 20:1, With the speed ball milling of 300 rev / mins 15 hours, this material is called material II; Material I and material II are according to the ratio of the amount of the material of bismuth salt in material I and the ratio of the amount of quaternary ammonium salt material in material II is 1: The proporti...

Embodiment 3

[0023] Example 3: Mix bismuth chloride, cobalt nitrate hexahydrate with a bismuth chloride content of 2%, copper acetate monohydrate with a bismuth chloride content of 1.8%, and perfluoroglutaric acid with a bismuth chloride content of 2% Then put into the ball mill, the mass ratio of the ball mill and the material is 20:1, ball mill for 20 hours at a speed of 390 rpm, this material is called material I; benzyltrimethylammonium fluoride, benzyltrimethylammonium 2% Span-80 of ammonium fluoride quality and 4% dehydrated alcohol of benzyltrimethylammonium fluoride quality are mixed and then put into a ball mill. The mass ratio of the ball mill to the material is 20:1. Minute speed ball milling 19 hours, this material is referred to as material II; Material I and material II are according to the ratio of the amount of material of bismuth salt in material I and the ratio of quaternary ammonium salt material in material II be 1: 3 ratio and Put the crystallization control agent poly...

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Abstract

The invention relates to a solid-phase synthesis bismuth fluoride lithium ion battery anode material with a Co<2+> and Cu<2+> doped structure and a preparation method of the solid-phase synthesis bismuth fluoride lithium ion battery anode material. The preparation method comprises the following steps: a quaternary ammonium salt taking fluoride as an anion is taken as a raw material, the raw material is in solid-phase synthesis into bismuth fluoride with an orthorhombic structure directly through steric hindrance of a macroradical and the action of a specific additive, and at the same time, the average discharge potential of the material is improved through Cu<2+> doping, and the electronic conductivity of the material is improved through Co<2+> doping, and the bismuth fluoride material is taken as a lithium ion battery anode material and has specific capacity exceeding 200 mAh.g<-1>. The preparation method is low in equipment requirement, the product is high in purity, reaction by-products such as various complex salts for producing bismuth fluoride in the solid-phase reaction can be avoided, and the solid-phase synthesis oxygen bearing bismuth fluoride anode material is excellent in 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): H01M4/136H01M4/1397H01M4/139H01M4/13H01M4/62
CPCH01M4/136H01M4/362H01M4/582H01M4/626H01M10/0525Y02E60/10
Inventor 徐玲霞水淼徐晓萍陈超陈姝舒杰任元龙
Owner NINGBO UNIV
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