A silicon-based negative electrode material with heterostructure, a preparation method thereof and a lithium ion battery are disclosed

A technology for lithium-ion batteries and negative electrode materials, applied in battery electrodes, secondary batteries, structural parts, etc., can solve problems such as unfavorable industrial production, increased internal resistance of batteries, poor battery cycle performance, etc., and achieve good cycle stability , Improve lithium storage performance and good rate performance

Active Publication Date: 2019-01-25
EVE ENERGY CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Although the silicon material has such great advantages, it has great defects in practical applications: (1) During the charging and discharging cycle of the silicon material, due to the large volume expansion (~300%), it is easy to cause the active material to break into powder; In addition, the expansion and contraction of silicon particles lead to the continuous rupture and formation of the surface SEI (Solid electrolyte interphase, solid electrolyte interface) film, which consumes the limited electrolyte and lithium in the positive electrode, causing the SEI film to thicken and the internal resistance of the battery to increase. Resulting in poor battery cycle performance; (2) As a semiconductor, silicon has much poorer conductivity than graphite, and the polarization is larger during charge and discharge, and the kinetic process is slower
[0008] However, the above-mentioned schemes all have the problem of cumbersome preparation methods and are not conducive to industrial production. Therefore, there is an urgent need in this field to develop an efficient preparation method that is simple, easy to achieve large-scale production, and has good product rate performance and cycle performance.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0085] In this example, a silicon-based negative electrode material with a heterogeneous structure is prepared according to the following method:

[0086] (1) Mix carbon nanotubes with mixed acid of sulfuric acid and hydrochloric acid (the mass ratio of sulfuric acid and hydrochloric acid is 1:1), the solid-liquid ratio of the mass of carbon nanotubes to the volume of mixed acid is 0.5g / L, condense and reflux at 100°C for 3h , followed by centrifugation, washing and vacuum-drying the obtained solid at 65° C. for 1 hour to obtain oxidized carbon nanotubes;

[0087] Wherein, the carbon nanotubes are multi-walled carbon nanotubes, the diameter of the carbon nanotubes is 5-15 nm, and the length of the carbon nanotubes is 10-20 μm;

[0088] (2) Ultrasonically disperse the oxidized carbon nanotubes in water for 1.2 hours in step (1), mix them with ethyl orthosilicate, and heat them in a water bath at 65°C for a reaction. The reaction time is 8 hours, and then centrifuged. Washing a...

Embodiment 2

[0096] In this example, a silicon-based negative electrode material with a heterogeneous structure is prepared according to the following method:

[0097] (1) Mix carbon nanotubes with a mixed acid of nitric acid and hydrochloric acid (the mass ratio of nitric acid to hydrochloric acid is 2:1), the solid-liquid ratio of the mass of carbon nanotubes to the volume of the mixed acid is 0.17g / L, and reflux at 80°C 1h, and then centrifuged, and the obtained solid was washed and vacuum-dried at 50°C, and the vacuum-drying time was 1h to obtain carbon dioxide nanotubes;

[0098] Wherein, the carbon nanotubes are multi-walled carbon nanotubes, the diameter of the carbon nanotubes is 10-15 nm, and the length of the carbon nanotubes is 5-10 μm;

[0099] (2) After ultrasonically dispersing the oxidized carbon nanotubes in water for 0.5 minutes in step (1), mix them with diallylphenyldimethylsilane, and heat them in a water bath at 50°C to react. The reaction time is 6 hours. Accompanied...

Embodiment 3

[0107] In this example, a silicon-based negative electrode material with a heterogeneous structure is prepared according to the following method:

[0108] (1) Mix the carbon nanotubes with the mixed acid of nitric acid and phosphoric acid (the mass ratio of nitric acid and hydrochloric acid is 1:3), the solid-liquid ratio of the mass of carbon nanotubes to the volume of the mixed acid is 1g / L, condense and reflux at 130°C for 5h , followed by centrifugation, washing the obtained solid and vacuum drying at 80° C. for 1 hour to obtain oxidized carbon nanotubes;

[0109] Wherein, the carbon nanotubes are multi-walled carbon nanotubes, the diameter of the carbon nanotubes is 15-20 nm, and the length of the carbon nanotubes is 20-30 μm;

[0110] (2) After ultrasonically dispersing the carbon dioxide nanotubes in step (1) in water for 2 hours, mix them with triethoxysilane, and heat them in a water bath at 80°C for a reaction. The reaction time is 10 hours, and the reaction is accom...

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Abstract

The invention provides a heterostructure silicon-based negative electrode material, a preparation method thereof and a lithium ion battery. The negative electrode material comprises carbon nanotubes,silicon distributed on the surface of the carbon nanotubes, and graphene coated on the silicon. 1) mixing that carbon nanotube and the acid, condensing and reflux, and then solid-liquid separation toobtain the carbon oxide nanotube; 2) after that carbon oxide nanotube is dispersed in wat, mixing with an organosilicon source, heating and reacting, and then solid-liquid separation; 3) mixing the product and the magnesium powder, crushing the mixture in an inert atmosphere, heating the mixture in an inert atmosphere, and heat treating the mixture; 4) under vacuum or inert atmosphere, taking carbon source as raw material to produce graphene by chemical vapor deposition on that product of the step 5) pickling to obtain the negative electrode material. The negative electrode material provided by the invention has good cycle stability and rate performance.

Description

technical field [0001] The invention belongs to the technical field of energy storage, and relates to a negative electrode material, in particular to a silicon-based negative electrode material with a heterogeneous structure, a preparation method thereof, and a lithium ion battery. Background technique [0002] With the wide application of consumer electronics and new energy vehicles, high specific energy lithium-ion batteries have become one of the research hotspots of researchers, and the capacity of materials directly affects the specific energy of batteries. At present, the theoretical gram capacity of commercial graphite-based negative electrode materials is only 372mAh / g, and its capacity has been developed and utilized to the limit. In comparison, the theoretical gram capacity of silicon materials is as high as 4200mAh / g (Li 4.4 Si). In addition, silicon also has a slightly higher lithium intercalation platform than graphite (0.2Vvs.Li + / Li), higher safety performa...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/38H01M4/583H01M4/62H01M10/0525C01B32/182
CPCC01B32/182H01M4/362H01M4/366H01M4/386H01M4/583H01M4/625H01M10/0525Y02E60/10
Inventor 何锐何巍刘金成袁中直
Owner EVE ENERGY CO LTD
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