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Silicon or silicon alloy composite lithium ion battery negative electrode material containing lithium bis(oxalate)borate as well as preparation method and application of negative electrode material

A technology of lithium bisoxalatoborate and lithium oxalateborate, which is applied in battery electrodes, secondary batteries, circuits, etc., can solve the problems of low solubility, low conductivity, poor low temperature performance and hygroscopicity, etc. Long cycle life, excellent film-forming ability, improved electrochemical performance

Inactive Publication Date: 2017-06-13
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the performance of lithium dioxalate borate is good and the improvement effect is obvious, it has not been widely used in the field of silicon-based negative electrode materials such as silicon particles, silicon alloys, and silicon-carbon materials in recent years. The low solubility, low conductivity, poor low-temperature performance and hygroscopicity of lithium diacid borate in the non-aqueous solvent of the electrolyte limit its further application

Method used

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  • Silicon or silicon alloy composite lithium ion battery negative electrode material containing lithium bis(oxalate)borate as well as preparation method and application of negative electrode material
  • Silicon or silicon alloy composite lithium ion battery negative electrode material containing lithium bis(oxalate)borate as well as preparation method and application of negative electrode material
  • Silicon or silicon alloy composite lithium ion battery negative electrode material containing lithium bis(oxalate)borate as well as preparation method and application of negative electrode material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Commercial silicon powder and high-purity iron powder were loaded into a high-energy ball mill filled with argon at a mass ratio of 9:1 for mechanical alloying, and ferrosilicon alloy powder was obtained after high-energy ball milling for 10 hours. Then ball mill the powder with citric acid and acetylene black at a mass ratio of 5:5:1, ball mill for 1 hour under an argon protective atmosphere, and then carbonize at 600°C for 30 minutes under a nitrogen-hydrogen mixed protective gas. The mass percentage of the carbon material was measured to be 19.5% by means of elemental testing and analysis. Then add 5% lithium bisoxalate borate, stir and mix to obtain a ferrosilicon alloy-18.6% carbon-4.7% lithium bisoxalate borate composite lithium ion battery negative electrode material.

[0054] figure 1 Scanning electron micrograph of the ferrosilicon alloy-18.6% carbon-4.7% bisoxalate lithium borate composite lithium ion battery negative electrode material prepared in Example 1 ...

Embodiment 2

[0060] Commercial silicon powder, sucrose, and acetylene black were mixed by high-energy ball milling at a mass ratio of 6:3.5:0.5, ball milled for 30 minutes under an argon protective atmosphere, and then carbonized at 700°C for 1 hour under a nitrogen-hydrogen mixed protective gas. The mass percentage of the carbon material was measured to be 10.9% by means of an elemental test and analysis method. Then add 1% lithium bisoxalate borate, stir and mix to obtain a silicon-10.9% carbon-1% lithium bisoxalate borate composite lithium ion battery negative electrode material. Figure 5 The cycle curve of the silicon-10.9% carbon-1% bisoxalate lithium borate composite lithium ion battery negative electrode material prepared in Example 2 of the present invention under the charge and discharge condition of 300 mA / g. Its first reversible (charging) capacity reaches 1858 mAh / g, and after 100 cycles, the capacity is 1411 mAh / g, and the capacity retention rate is 75.9%, showing excellent c...

Embodiment 3

[0063] Commercial silicon powder and nickel powder are smelted at high temperature under argon protective gas at a mass ratio of 3:2, followed by high-temperature atomization to obtain silicon-nickel alloy powder. Then the powder and vapor-phase-grown carbon fiber were mixed by high-energy ball milling at a mass ratio of 7:3, ball milled for 16 hours under an argon protective atmosphere, and then 10% by mass percentage of lithium dioxalate borate was added for stirring and mixing to obtain A silicon-nickel alloy-27.3% carbon-9.1% lithium bisoxalate borate composite lithium-ion battery negative electrode material. Figure 6 For the XRD test results of the silicon-nickel alloy-27.3% carbon-9.1% lithium dioxalate borate composite lithium ion battery negative electrode material prepared in Example 3 of the present invention, obvious silicon and nickel elements can be seen from the figure, and there are Nickel-silicon alloy formation. Figure 7 The cycle curve of the silicon-nicke...

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Abstract

The invention belongs to the technical field of energy materials and energy conversion and in particular relates to a silicon-based lithium ion battery composite negative electrode material, a negative electrode using the material, and a lithium ion battery. The silicon or silicon alloy composite lithium ion battery negative electrode material containing lithium bis(oxalate)borate contains 1-20 mass percent of lithium bis(oxalate)borate (LiBOB). The negative electrode material disclosed by the invention is obtained by adding lithium bis(oxalate)borate into a silicon or silicon alloy-carbon composite lithium ion battery negative electrode material, or is obtained by introducing the lithium bis(oxalate)borate in the process of preparing the battery negative electrode material. According to the battery negative electrode material, the highest first charge and discharge capacity can reach 1800-2000 mAh per gram, the capacity after 100 times of cycle can reach 1200-1500 mAh per gram, and the capacity retention ratio reaches 69-85%.

Description

technical field [0001] The invention belongs to the technical field of energy materials and energy conversion, and in particular relates to a silicon-based lithium ion battery composite negative electrode material, a negative electrode using the material and a lithium ion battery. Background technique [0002] With the rapid development and progress of modern society, the appearance of portable and mobile electronic devices has greatly improved people's lives, among which the key lithium-ion battery technology has been more and more widely used and valued, and it is urgent to develop a light-weight , Lithium-ion batteries with small volume, high capacity and high energy density. Graphite negative electrode materials are widely used in the production of lithium-ion batteries due to their high cycle efficiency and excellent cycle performance, but their lithium storage capacity is low, and the lithium intercalation potential is close to the lithium potential. High-speed chargin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/38H01M10/0525
CPCH01M4/364H01M4/386H01M10/0525Y02E60/10
Inventor 潘洪革吴相欣高明霞刘永锋
Owner ZHEJIANG UNIV
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