高分散SiO2/石油沥青基多孔碳用于锂离子电池负极

doi:10.11949/0438-1157.20191370

化工学报 ›› 2020, Vol. 71 ›› Issue (6): 2752-2759.DOI: 10.11949/0438-1157.20191370

• 材料化学工程与纳米技术 • 上一篇下一篇

高分散SiO₂/石油沥青基多孔碳用于锂离子电池负极

夏争争¹(),刘加亮¹,牛建杰¹,胡涵¹,赵青山¹(),吴明铂²()

^1.中国石油大学(华东)化学工程学院，重质油国家重点实验室，山东青岛 266580
^2.中国石油大学(华东)石大兖矿新能源学院, 山东青岛 266580

收稿日期:2019-11-11 修回日期:2020-02-03 出版日期:2020-06-05 发布日期:2020-06-05
通讯作者: 赵青山,吴明铂
作者简介:夏争争（1995—），男，硕士研究生，1515926489@qq.com
基金资助:
山东省自然科学基金项目(ZR2019QB016);山东省自然科学基金重大基础研究项目(ZR2018ZC1458);中央高校基本科研业务费专项资金(18CX02015A)

Highly dispersed SiO₂/petroleum pitch-derived porous carbon composite as anode material for lithium-ion batteries

Zhengzheng XIA¹(),Jialiang LIU¹,Jianjie NIU¹,Han HU¹,Qingshan ZHAO¹(),Mingbo WU²()

^1.State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^2.College of New Energy, China University of Petroleum (East China), Qingdao 266580, Shandong, China

Received:2019-11-11 Revised:2020-02-03 Online:2020-06-05 Published:2020-06-05
Contact: Qingshan ZHAO,Mingbo WU

摘要/Abstract

摘要：

二氧化硅(SiO₂)作为锂离子电池负极材料具有理论容量高、放电电位低、成本较低等特点，但存在导电性差、充放电过程体积膨胀严重以及容量衰减过快等问题。以石油沥青为碳源，利用硅烷偶联剂KH-540对纳米α-Fe₂O₃模板剂进行表面化学包覆，然后将硅源修饰模板剂与碳源混合，经碳化、酸洗等步骤得到高分散SiO₂/石油沥青基多孔碳(SiO₂/PC)。所得SiO₂/PC作为锂离子电池负极材料，在1 A·g^-1电流密度下，循环900圈后仍具有640 mA·h·g^-1的高可逆比容量。研究结果表明，高度纳米化的SiO₂在高温碳化过程原位生成，紧密牢固地负载于多孔碳表面，提高了其导电性，同时能够有效缓解SiO₂在充放电过程中的体积膨胀，抑制SiO₂的团聚或粉化，从而表现出优异的电化学性能。

关键词: 锂离子电池, 负极材料, 高分散SiO₂, 石油沥青, 多孔碳

Abstract:

Silicon dioxide (SiO₂) as anode material for lithium ion batteries has the characteristics of high theoretical capacity, low discharge potential, and low cost. However, its poor conductivity, severe volume expansion during charge and discharge processes, and rapid capacity decay hinders the practical application. By employing petroleum asphalt as the carbon source, silane coupling agent (KH-540) surface modified α-Fe₂O₃as the template, highly dispersed SiO₂/petroleum-based porous carbon composite (SiO₂/PC) was prepared through carbonization, acid pickling procedures. Serving as anode material for lithium ion batteries, the prepared SiO₂/PC exhibited excellent specific capacity and cyclability. The battery delivers a reversible specific capacity of 640 mA·h·g^-1 after 900 cycles at a high current density of 1 A·g^-1. The results show that the highly dispersed SiO₂ was in-situ formed during the carbonization process, which could be tightly and firmly immobilized on the porous carbon surface. Such structure can efficiently prevent the agglomeration/pulverizationof SiO₂and buffer the volume expansion during charge and discharge processes, leading to the excellent electrochemical performance.

Key words: lithium-ion battery, anode material, highly-dispersed SiO₂, petroleum pitch, porous carbon

中图分类号:

TQ 028.8

夏争争, 刘加亮, 牛建杰, 胡涵, 赵青山, 吴明铂. 高分散SiO₂/石油沥青基多孔碳用于锂离子电池负极[J]. 化工学报, 2020, 71(6): 2752-2759.

Zhengzheng XIA, Jialiang LIU, Jianjie NIU, Han HU, Qingshan ZHAO, Mingbo WU. Highly dispersed SiO₂/petroleum pitch-derived porous carbon composite as anode material for lithium-ion batteries[J]. CIESC Journal, 2020, 71(6): 2752-2759.

图/表 7

图1 样品SiO2/PC、PC、PCA(a)和样品SiO2/PC、改性模板Si@Fe2O3(b)的XRD谱图

Fig.1 XRD patterns of SiO2/PC, PC, PCA (a), SiO2/PC and Si@Fe2O3(b)

图2 样品PCA(a)、PC（b）和SiO2/PC(c)的SEM图；PC(d)、SiO2/PC(e)的TEM图; SiO2/PC的HR-TEM图(f)

Fig.2 SEM images of PCA (a), PC（b）and SiO2/PC(c); TEM images of PC(d), SiO2/PC (e); HR-TEM image of SiO2/PC(f)

图3 SiO2/PC(a)和PC(b)的氮气吸附-脱附等温线

Fig.3 N2 adsorption-desorption isotherms curves of SiO2/PC (a) and PC (b)

图4 样品PCA、PC和SiO2/PC的XPS总谱(a)~(c)和样品SiO2/PC总谱中Si 2p高分辨率谱图(d)

Fig.4 Full range XPS spectra of PCA, PC and SiO2/PC(a) ~ (c). XPS spectra of C 1s, O 1s and Si 2p regions of SiO2/PC(d)

图5 样品SiO2/PC、PC、PCA的Raman谱图

Fig.5 Raman spectra of SiO2/PC, PC and PCA

图6 样品SiO2/PC的循环伏安曲线(a)，长循环性能(b)和不同电流密度下的倍率性能(c)，样品SiO2/PC、PC、PCA 以及Pristine SiO2在1 A·g-1电流密度下的循环性能对比(d)

Fig.6 CV curves (a), cycling performance(b) and rate performance (c) of SiO2/PC. Cycling performance of SiO2/PC, PC and PCA at 1 A·g-1 (d)

图7 样品SiO2/PC与PC、PCA的交流阻抗对比

Fig.7 Nyquist EIS plots of SiO2/PC, PC and PCA

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高分散SiO₂/石油沥青基多孔碳用于锂离子电池负极

Highly dispersed SiO₂/petroleum pitch-derived porous carbon composite as anode material for lithium-ion batteries

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