纳米Si掺杂SiO<i><sub>x</sub></i>-Si@C@碳纳米管复合负极材料的制备及性能

李文超; 唐仁衡; 肖方明; 黄玲; 王英

doi:10.13801/j.cnki.fhclxb.20191206.005

纳米Si掺杂SiO_x-Si@C@碳纳米管复合负极材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20191206.005

1.
广东省稀土开发及应用重点实验室，广州 510650
2.
广东省稀有金属研究所，广州 510650

基金项目: 广东省科学院专项资金(2019GDASYL-0501008)；广州市科技计划(201802020029)；广东省自然科学基金(2014A030308015)；广东省省级科技计划(2015B010116002)

详细信息

通讯作者:
王英，硕士，教授级高工，研究方向为锂离子电池材料　E-mail：wy2228086@163.com

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2019-08-27
- 录用日期: 2019-11-12
- 网络出版日期: 2019-12-06
- 刊出日期: 2020-08-15

Preparation and properties of nano-Si doped SiO_x-Si@C@carbon nanotubes composite anode materials

1.
Guangdong Province Key Laboratory of Rare Earth Development and Application, Guangzhou 510650, China
2.
Guangdong Research Institute of Rare Metals, Guangzhou 510650, China

摘要

摘要: 在对氧化亚硅(SiO)材料进行表面碳包覆和添加导电材料的基础上，掺杂少量纳米Si进一步提高其首次充放电容量和首次库仑效率。采用XRD、SEM、TEM、Raman、FTIR分析材料的物相结构和微观形貌，通过恒流充放电测试仪分析复合材料的电化学性能。结果显示，纳米Si质量为SiO_x质量10%的复合材料(SiO_x-Si@C@碳纳米管(CNTs)-10)的首次充放电容量分别为1 348.1 mA•h/g和1 874.4 mA•h/g，首次库仑效率为71.9%，循环100周后材料的可逆容量为1 116.2 mA•h/g，容量保持率为82.8%；以不同电流密度充放电，其放电容量远远高于没有纳米Si掺杂的材料。SiO_x-Si@C@CNTs复合材料具有较高的首次库伦效率、较好的循环性能和倍率性能。
- 锂离子电池 /
- SiO_x-Si@C@CNTs复合材料 /
- 纳米Si /
- 库仑效率 /
- 循环性能
Abstract: Based on the carbon coating and addition of conductive materials, a small amount of nano-Si was doped to further improve the first charge and discharge capacity and the first coulombic efficiency. The phase structure and micromorphology of the materials were analyzed by XRD, SEM, TEM, Raman and FTIR, and the electrochemical properties of the composites were analyzed by a constant current charge-discharge test. The results show that the composites with 10% nano-Si (SiO_x-Si@C@carbon nanotubes(CNTs)-10) exhibit a first charge and discharge capacity of 1 348.1 mA•h/g and 1 874.4 mA•h/g, respectively, with the first coulombic efficiency of 71.9%. After 100 cycles, the reversible capacity of the composite is 1 116.2 mA•h/g, with the capacity retention rate of 82.8%. The discharge capacity is much higher than that of the material without nano-Si doping at different current densities. The SiO_x-Si@C@CNTs composites show high first coulombic efficiency, good cycle performance and rate performance.
- lithium ion battery /
- SiO_x-Si@C@CNTs composite /
- nano-Si /
- coulombic efficiency /
- cycle performance

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图 1 SiO_x@C@CNTs、SiO_x-Si@C@CNTs-5、SiO_x-Si@C@CNTs-10和SiO_x-Si@C@CNTs-15复合材料的XRD图谱（a）、拉曼光图谱（b）和FTIR图谱（c）

Figure 1. XRD patterns (a), Raman spectra (b) and FTIR spectra (c) of SiO_x@C@CNTs, SiO_x-Si@C@CNTs-5, SiO_x-Si@C@ CNTs-10 and SiO_x-Si@C@CNTs-15 composites

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图 2 SiO_x@C@CNTs((a)、(b))、 SiO_x-Si@C@CNTs-5((c)、(d))、 SiO_x-Si@C@CNTs-10((e)、(f))和 SiO_x-Si@C@CNTs-15((g)、(h))复合材料的SEM图像

Figure 2. SEM images of SiO_x@C@CNTs ((a),(b)), SiO_x-Si@C@CNTs-5 ((c),(d), SiO_x-Si@C@CNTs-10 ((e),(f)) and SiO_x-Si@C@CNTs-15 ((g),(h)) composites

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图 3 SiO_x-Si@C@CNTs-10复合材料的TEM图像((a)~(c))和EDS元素扫描图(d)

Figure 3. TEM images ((a)-(c)) and EDS element mapping (d) of SiO_x-Si@C@CNTs-10 composite

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图 4 SiO_x@C@CNTs, SiO_x-Si@C@CNTs-5, SiO_x-Si@C@CNTs-10和SiO_x-Si@C@CNTs-15的循环性能（（a）~（d））和倍率性能（e）,SiO_x-Si@C@CNTs-10的不同循环次数的充放电曲线（f）

Figure 4. Cycling performance ((a)-(d)) and rate performance (e) of SiO_x@C@CNTs, SiO_x-Si@C@CNTs-5, SiO_x-Si@C@CNTs-10 and SiO_x-Si@C@CNTs-15 composites at various current densities and discharge/charge curves of SiO_x-Si@C@CNTs-10 at different cycle numbers (f)

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图 5 SiO_x-Si@C@CNTs-10复合材料的交流阻抗曲线（a）和循环伏安曲线（b）

Figure 5. Nyquist plots(a) and cycle voltammetry curves(b) of SiO_x-Si@C@CNTs-10 composite

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图 6 SiO_x-Si@C@CNTs-10复合材料电极充放电前及100周后的SEM图像

Figure 6. SEM images of SiO_x-Si@C@CNTs-10 composite electrode before and after 100 cycles charge/discharge

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表 1 SiO_x-Si@C@CNTs复合材料中增强相的含量

Table 1. Contents of reinforcing phases in SiO_x-Si@C@CNTs composites

Composite	SiO_x/g	Nano-Si/g	C/g	CNTs/g
SiO_x@C@CNTs	400	0	80	8
SiO_x-Si@C@CNTs-5	400	20	80	8
SiO_x-Si@C@CNTs-10	400	40	80	8
SiO_x-Si@C@CNTs-15	400	60	80	8
Notes: CNTs—Carbon nanotubes.

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参考文献(24)

[1]	HONG L, WANG Z, CHEN L, et al. Research on advanced materials for Li-ion batteries[J]. Advanced Materials,2010,21(45):4593-4607.
[2]	GE M, RONG J, FANG X, et al. Porous doped silicon nanowires for lithium ion battery anode with long cycle life[J]. Nano Letters,2012,12(5):2318-2323. doi: 10.1021/nl300206e
[3]	JEONG S, LI X, ZHENG J, et al. Hard carbon coated nano-Si/graphite composite as a high performance anode for Li-ion batteries[J]. Journal of Power Sources,2016,329:323-329. doi: 10.1016/j.jpowsour.2016.08.089
[4]	FEI D, SHI L, SONG P, et al. Design of orderly carbon coatings for SiO anodes promoted by TiO<sub>2</sub> toward high performance lithium-ion battery[J]. Chemical Engineering Journal,2018,338:488-495. doi: 10.1016/j.cej.2018.01.048
[5]	PAN K, ZOU F, CANOVA M, et al. Systematic electrochemical characterizations of Si and SiO anodes for high capacity Li-ion batteries[J]. Journal of Power Sources,2019,413:20-28. doi: 10.1016/j.jpowsour.2018.12.010
[6]	PARK C M, CHOI W, HWA Y, et al. Characterizations and electrochemical behaviors of disproportionated SiO and its composite for rechargeable Li-ion batteries[J]. Journal of Materials Chemistry,2010,20(23):4854-4860. doi: 10.1039/b923926j
[7]	LIU Z, YU Q, ZHAO Y, et al. Silicon oxides: A promising family of anode materials for lithium-ion batteries[J]. Chemical Society Reviews,2019,48(1):285-309. doi: 10.1039/C8CS00441B
[8]	WU W, WANG M, WANG R, et al. Magnesio-mechanochemical reduced SiO for high-performance lithium ion batteries[J]. Journal of Power Sources,2018,407:112-122. doi: 10.1016/j.jpowsour.2018.10.065
[9]	XU D, CHEN W, LUO Y, et al. Amorphous TiO<sub>2</sub> layer on silicon monoxide nanoparticles as stable and scalable core-shell anode materials for high performance lithium ion batteries[J]. Applied Surface Science,2019,479:980-988. doi: 10.1016/j.apsusc.2019.02.156
[10]	YANG W, LIU H, REN Z, et al. A novel multielement, multiphase, and B-containing SiO<sub>x</sub> composite as a stable anode material for Li-ion batteries[J]. Advanced Materials Interfaces,2019,6:1801631. doi: 10.1002/admi.201801631
[11]	DOH C H, SHIN H M, KIM D H, et al. Improved anode performance of thermally treated SiO/C composite with an organic solution mixture[J]. Electrochemistry Communications,2008,10(2):233-237. doi: 10.1016/j.elecom.2007.11.034
[12]	LEE D J, RYOU M H, LEE J N, et al. Nitrogen-doped carbon coating for a high-performance SiO anode in lithium-ion batteries[J]. Electrochemistry Communications,2013,34(5):98-101.
[13]	SI Q, HANAI K, ICHIKAWA T, et al. Improvement of cyclic behavior of a ball-milled SiO and carbon nanofiber composite anode for lithium-ion batteries[J]. Journal of Power Sources,2011,196(22):9774-9779. doi: 10.1016/j.jpowsour.2011.08.005
[14]	LIU W R, YEN Y C, WU H C, et al. Nano-porous SiO/carbon composite anode for lithium-ion batteries[J]. Journal of Applied Electrochemistry,2009,39(9):1643-1649. doi: 10.1007/s10800-009-9854-x
[15]	李文超, 唐仁衡, 王英, 等. 锂离子电池SiO<italic><sub>x</sub></italic>/C@CNTs复合负极材料的制备及其电化学性能[J]. 材料导报, 2018, 32(17):2920-2924. doi: 10.11896/j.issn.1005-023X.2018.17.004 LI Wenchao, TANG Renheng, WANG Ying, et al. Preparation and electrochemical performance of SiO<italic><sub>x</sub></italic>/C@CNTs composite anode for Lithium ion batteries[J]. Materials Reports,2018,32(17):2920-2924(in Chinese). doi: 10.11896/j.issn.1005-023X.2018.17.004
[16]	REN Y, LI M. Si-SiO<sub>x</sub>-cristobalite/graphite composite as anode for Li-ion batteries[J]. Electrochimica Acta,2014,142(142):11-17.
[17]	IZAWA T A, ADITYA F T, SHUTO K, et al. Improving the performance of Li-ion battery carbon anodes by in-situ immobilization of SiO<italic>x</italic> nanoparticles[J]. Materials Research Bulletin,2019,112:16-21. doi: 10.1016/j.materresbull.2018.11.044
[18]	窦一博, 高明霞, 刘永锋. 高性能Si@SiO<sub>x</sub>@C负极材料的制备及其电化学性能[J]. 材料科学与工程学报, 2016, 34(1):25-31. DOU Yibo, GAO Mingxia, LIU Yongfeng. Synthesis of high-performance Si@SiOx@C anode materials and their electrochemical properties[J]. Journal of Materials Science <italic>&</italic> Engineering,2016,34(1):25-31(in Chinese).
[19]	GAN C, WEN S, LIU Y, et al. Preparation of Si-SiO<sub>x</sub> nanoparticles from volatile residue produced by refining of silicon[J]. Waste Management,2019,84:373-382. doi: 10.1016/j.wasman.2018.11.032
[20]	PARK YK, MATHEW B, GYEONG S, et al. Synthesis of Si/SiO<italic><sub>x</sub></italic> from talc and its characteristics as an anode for lithiumion batteries[J]. Journal of Electroanalytical Chemistry,2019,833:552-559. doi: 10.1016/j.jelechem.2018.12.037
[21]	YOM J H, SUN W H, CHO S M, et al. Improvement of irreversible behavior of SiO anodes for lithium ion batteries by a solid state reaction at high temperature[J]. Journal of Power Sources,2016,311:159-166. doi: 10.1016/j.jpowsour.2016.02.025
[22]	YANG X, WEN Z, XU X, et al. Nanosized silicon-based composite derived by in situ mechanochemical reduction for lithium ion batteries[J]. Journal of Power Sources,2007,164(2):880-884. doi: 10.1016/j.jpowsour.2006.11.010
[23]	WU W, LIANG Y, MA H, et al. Insights into the conversion behavior of SiO-C hybrid with pretreated graphite as anodes for Li-ion batteries[J]. Electrochimica Acta,2016,187:473-479. doi: 10.1016/j.electacta.2015.11.008
[24]	TAN H G, DUH J G. Processing silicon microparticles recycled from wafer waste via rapid thermal process for lithium-ion battery anode materials[J]. Journal of Power Sources,2016,335:146-154. doi: 10.1016/j.jpowsour.2016.10.034