锂离子电池负极材料Si@C/SiOx的制备及其电化学性能

doi:10.15541/jim20160516

无机材料学报 ›› 2017, Vol. 32 ›› Issue (7): 699-704.DOI: 10.15541/jim20160516

锂离子电池负极材料Si@C/SiO_x的制备及其电化学性能

杨桃^1,2, 李肖^1,2, 田晓冬^1,2, 宋燕¹, 刘占军¹, 郭全贵¹

(1. 中国科学院山西煤炭化学研究所, 中国科学院炭材料重点实验室, 太原 030001; 2. 中国科学院大学, 北京100049)

收稿日期:2016-09-18 修回日期:2016-12-29 出版日期:2017-07-20 网络出版日期:2017-06-23
作者简介:杨桃(1991–), 女, 硕士研究生. E-mail: taomung@126.com
基金资助:
国家自然科学基金(50602046, U610119, U1610252);山西省自然科学基金(2012011219-3);山西省重点研发计划(201603D3112007);中国科学院山西煤炭化学研究所杰出青年人才项目(Y2SC921751);中国科学院青年创新促进会资助(118800QCH1)

Preparation and Electrochemical Performance of Si@C/SiO_x as Anode Material for Lithium-ion Batteries

YANG Tao^1,2, LI Xiao^1,2, TIAN Xiao-Dong^1,2, SONG Yan¹, LIU Zhan-Jun¹, GUO Quan-Gui¹

(1. CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China)

Received:2016-09-18 Revised:2016-12-29 Published:2017-07-20 Online:2017-06-23
About author:YANG Tao. E-mail: taomung@126.com
Supported by:
National Natural Science Foundation of China (50902046, U1610119, U1610252);Natural Science Foundation of Shanxi Province (2012011219-3);Key Research and Development Program of Shanxi Province (201603D3112007);Outstanding Young Scientist Fund of Institute of Coal Chemistry (Y2SC921751);Youth Innovation Promotion Association (118800QCH1)

摘要/Abstract

摘要：

硅理论比容量高, 放电平台低, 是商业化锂离子电池石墨负极的替代材料之一, 但是其充放电循环中体积变化大, 容量衰减迅速, 制约了其商业化使用。本研究通过一步法制备了具有核壳结构的硅@碳/硅氧化物(Si@C/SiO_x), 将其作为锂离子电池负极材料。采用SEM、TEM、XRD、XPS等手段对所制备材料的微观形貌、结构以及组分进行了分析, 并对其进行了相关的电化学测试。结果表明, Si@C/SiO_x核壳材料比Si@C核壳材料具备更优良的电化学性能。在200 mA/g电流密度下, 循环45次后, Si@C的容量保持率为60.2%; 而当C/SiO_x作为Si核外壳时, 200 mA/g电流密度下, 循环45次后, Si@C/SiO_x比容量值为787.2 mAh/g, 容量保持率提高到87.3%。这主要是由于C与SiO_x复合后, 外壳的机械强度大于碳壳, 能够较好地缓冲Si体积膨胀产生的巨大应力, 从而保证结构的完整性, 提高了硅基负极材料的商业化应用的可能性。

null

关键词: 锂离子电池, 硅@碳/硅氧化物复合材料, 核壳结构, 循环稳定性

Abstract:

Silicon is one of candidates for graphite anode on account of its high theoretical specific capacity and low discharge plateau. But, the severe decay caused by huge volume change during the process of charge/discharge hinders the realization of Si commercial use in lithium-ion batteries (LIBs). A new material named Si@C/SiO_x nanocomposite with core-shell structure was prepared via a facile one-step method and used as anode material for LIBs. The micromorphology, structure and electrochemical performance of Si@C/SiO_x nanomaterial were investigated by SEM, TEM, XRD, and XPS measurements. It is found that the electrochemical performance of Si@C/SiO_x is better than Si@C core-shell nanomaterial. After 45 cycles at current density of 200 mA/g, the capacity retentions of Si@C electrode and Si@C/SiO_x electrode are 60.2% and 87.3%, respectively, and the reversible capacity of Si@C/SiO_x electrode remains 787.2 mAh/g. The electrochemical performance improvement of Si@C/SiO_x electrode is ascribed to the combination of carbon and SiO_x, which maintains the integrity of electrode structure through buffering the big pressure more effectively. And it improves the possibility of commercial use for Si anodes.

Key words: lithium-ion batteries, Si@C/SiOx nanocomposite, core-shell structure, cycle stability

中图分类号:

TQ15

杨桃, 李肖, 田晓冬, 宋燕, 刘占军, 郭全贵. 锂离子电池负极材料Si@C/SiO_x的制备及其电化学性能[J]. 无机材料学报, 2017, 32(7): 699-704.

YANG Tao, LI Xiao, TIAN Xiao-Dong, SONG Yan, LIU Zhan-Jun, GUO Quan-Gui. Preparation and Electrochemical Performance of Si@C/SiO_x as Anode Material for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2017, 32(7): 699-704.

图/表 6

图1 (a) Si纳米颗粒、(b) Si@C核壳材料和(c) Si@C/SiOx核壳材料的SEM照片

Fig. 1 SEM images of (a) pristine Si, (b) Si@C and (c) Si@C/SiOx core-shell nanoparticles

图2 (a)Si@C和(b)Si@C/SiOx核壳材料的TEM照片

Fig. 2 TEM images of (a) Si@C and (b) Si@C/SiOx core-shell nanoparticles

图3 (a)Si、(b)Si@C以及(c)Si@C/SiOx材料的XRD图谱

Fig. 3 XRD patterns of (a) Si, (b) Si@C and (c) Si@C/SiOx nanoparticles

图4 Si@C/SiOx和Si@C核壳材料的XPS谱图(a), 以及Si@C(b)和Si@C/SiOx(c)核壳材料的Si2p轨道高分辨XPS谱图

Fig. 4 XPS spectra for Si@C and Si@C/SiOx (a), high-resolution XPS spectrum of the Si2p peak for Si@C (b) and Si@C/SiOx (c)

图5 室温下, Si@C/SiOx 在0.01~3.0 V之间的循环伏安曲线

Fig. 5 CV curves of Si@C/SiOx nanocomposites in the range of 0.01-3.0 V at room temperature

图6 (a)Si@C/SiOx核壳材料的恒流充放电曲线, (b)Si@C和Si@C/SiOx核壳材料的循环性能, (c)Si@C以及Si@C/SiOx核壳材料在200 mA/g电流密度下循环测试时的容量保持率, (d)Si@C以及Si@C/SiOx核壳材料的倍率性能

Fig. 6 (a) Galvanostatic charge-discharge profiles of Si@C/SiOx, (b) cycle performance of Si@C and Si@C/SiOx, (c) capacity retention of Si@C and Si@C/SiOx measured at 200 mA/g, and (d) rate capacity of Si@C and Si@C/SiOx nanocompositesAll electrochemical performance is measured at room temperature

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锂离子电池负极材料Si@C/SiO_x的制备及其电化学性能

Preparation and Electrochemical Performance of Si@C/SiO_x as Anode Material for Lithium-ion Batteries

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锂离子电池负极材料Si@C/SiOx的制备及其电化学性能

Preparation and Electrochemical Performance of Si@C/SiOx as Anode Material for Lithium-ion Batteries

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锂离子电池负极材料Si@C/SiO_x的制备及其电化学性能

Preparation and Electrochemical Performance of Si@C/SiO_x as Anode Material for Lithium-ion Batteries