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High-conductivity sulfur-based positive electrode material for secondary battery and secondary battery

A secondary battery, high conductivity technology, applied in the direction of secondary batteries, battery electrodes, positive electrodes, etc., can solve the problem of low cycle stability and rate performance, which affects the use of secondary batteries, and the conductivity of S@pPAN positive electrode materials Low-level problems, to achieve the effects of cycle stability and rate performance improvement, strong practicability, and high crystallinity

Active Publication Date: 2021-12-17
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, when the traditional random polyacrylonitrile is used as the precursor, the electrical conductivity of the S@pPAN cathode material is low, about 10 -7 -10 -4 On the order of S / cm, the cycle stability and rate performance of the material are not high, which affects the use of secondary batteries

Method used

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  • High-conductivity sulfur-based positive electrode material for secondary battery and secondary battery
  • High-conductivity sulfur-based positive electrode material for secondary battery and secondary battery
  • High-conductivity sulfur-based positive electrode material for secondary battery and secondary battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] 30g of anhydrous CoCl 2 It was put into a three-necked flask, and after cooling in ice water for 30 min, the flask was filled with argon. Then 7g of acrylonitrile monomer and 0.15g of AIBN initiator were added, and the polymerization reaction was started at 60°C under magnetic stirring for 4h. After 6h of reaction, alternately washed with methanol and water, and then the obtained white powder was dried in a vacuum oven. After 24h, high isotactic polyacrylonitrile (the isotactic ratio of 55%) was obtained.

[0056] figure 1 and 2 The SEM and TEM images of the high isotactic polyacrylonitrile and the positive electrode material prepared in this example and the 1 random polyacrylonitrile and sulfur-based positive electrode material S@pPAN in the comparative example, it can be found that the particles of high isotactic polyacrylonitrile The diameter distribution is more uniform, the sphericity is better, and the surface is smoother.

[0057] like image 3 As shown, the...

Embodiment 2

[0061] 30g of anhydrous CoCl 2 It was put into a three-necked flask, and after cooling in ice water for 30 min, the flask was filled with argon. Then 7g of acrylonitrile monomer and 0.15g of AIBN initiator were added, and the polymerization reaction was started at 70°C under magnetic stirring for 4h. After 6h of reaction, alternately washed with methanol and water, and then the obtained white powder was dried in a vacuum oven. After 24h, high isotactic polyacrylonitrile (the isotactic ratio of 55%) was obtained.

[0062] High isotactic polyacrylonitrile, the isotonic ratio is much higher than that of random polyacrylonitrile, and the morphology is more regular, so its crystallinity is also much higher than that of random polyacrylonitrile, which is the corresponding group ( -AN) and the characteristic peaks of the material are shifted, such as Figure 4-5 shown.

[0063] Image 6 According to the DSC spectrogram analysis results of the high isotactic polyacrylonitrile prep...

Embodiment 3

[0067] 30g of anhydrous CoCl 2 It was put into a three-necked flask, and after cooling in ice water for 30 min, the flask was filled with argon. Then 7g acrylonitrile monomer and 0.15g AIBN initiator were added, and the polymerization reaction was started at 70°C under magnetic stirring for 4h. After 6h of reaction, the white powder was washed alternately with methanol and water, and then the obtained white powder was dried in a vacuum oven. After 24h, high isotactic polyacrylonitrile (the isotactic ratio of 55%) was obtained.

[0068] 2 g of the obtained high isotactic polyacrylonitrile and 16 g of elemental sulfur were added to ethanol for ball milling for 3 h, and after drying, the obtained powder was heated in a tube furnace at 350 °C for 5 h under a nitrogen atmosphere to obtain sulfur-based cathode material S@pPAN , the sulfur content in the material is 40.20wt%, and the electronic conductivity of the material is 6.7×10 -5 S / cm.

[0069] The battery assembly and test ...

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Abstract

The invention relates to a high-conductivity sulfur-based positive electrode material for a secondary battery and the secondary battery. The sulfur-based positive electrode material is formed by uniformly mixing highly isotactic polyacrylonitrile as a precursor with elemental sulfur and heating to generate chemical reaction; the highly isotactic polyacrylonitrile is synthesized by carrying out free radical polymerization or inclusion polymerization reaction on an acrylonitrile monomer under the action of a template agent. Compared with the prior art, the highly isotactic polyacrylonitrile has higher crystallinity and lower thermal cracking and cyclization temperature than random polyacrylonitrile, the conductivity of the prepared sulfur-based positive electrode material S@pPAN reaches 10<-3> S / cm, and the sulfur content is 40-70 wt%; when the material is used as a secondary battery positive electrode material, the overall conductivity of the material is remarkably improved, the active substance utilization rate, the cycling stability and the rate capability of a sulfur positive electrode are remarkably improved, and the reversible specific capacity of the positive electrode material exceeds 700 mAh / g; and the effects are obvious, the preparation process is simple, easy to amplify and high in practicability.

Description

technical field [0001] The invention relates to a sulfur-based positive electrode material, in particular to a high-conductivity sulfur-based positive electrode material for a secondary battery and a lithium-sulfur battery, a sodium-sulfur battery, a potassium-sulfur battery, a magnesium-sulfur battery, and a lithium-sulfur battery assembled with a sulfur-based positive electrode material. Sulfur batteries, calcium-sulfur batteries, and aluminum-sulfur batteries. Background technique [0002] Secondary batteries with lithium, sodium, potassium, magnesium or aluminum as the negative electrode and sulfur as the positive electrode have significant advantages such as high energy density, abundant sulfur resources, low cost, and environmental optimization. Taking lithium-sulfur batteries as an example, they have received extensive attention due to their theoretical energy density as high as 2600 Wh / kg, low cost and environmental friendliness. However, due to the insulating prope...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/38H01M4/62H01M10/052H01M10/054C08F8/48C08F120/44
CPCH01M4/38H01M4/624H01M10/052H01M10/054C08F8/48H01M2004/021H01M2004/028C08F120/44Y02E60/10H01M4/604C08F20/44H01M4/5815H01M4/136H01M4/625H01M4/1397C08F2810/00
Inventor 王久林雷靖宇路会超杨军
Owner SHANGHAI JIAO TONG UNIV
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