Si@环化聚丙烯腈/多壁碳纳米管负极复合材料的制备及电化学性能

魏成成; 孙晓刚; 梁国东; 黄雅盼; 胡浩; 徐宇浩

doi:10.13801/j.cnki.fhclxb.20191031.002

Si@环化聚丙烯腈/多壁碳纳米管负极复合材料的制备及电化学性能

doi: 10.13801/j.cnki.fhclxb.20191031.002

魏成成¹,
孙晓刚^{1, 2, ,},
梁国东¹,
黄雅盼¹,
胡浩¹,
徐宇浩¹

1.
南昌大学　机电工程学院，南昌 330031
2.
江西克莱威纳米碳材料有限公司，南昌 330031

基金项目: 江西省科技厅资助项目(20142BBE50071)；江西省教育厅资助项目(KJLD13006)

详细信息

通讯作者:
孙晓刚，教授，研究方向为碳纳米管和锂离子电池　E-mail：xiaogangsun@163.com

中图分类号: TB383；TM911
计量
- 文章访问数: 1013
- HTML全文浏览量: 180
- PDF下载量: 54
- 被引次数: 0
出版历程
- 收稿日期: 2019-07-20
- 录用日期: 2019-10-30
- 网络出版日期: 2019-10-31
- 刊出日期: 2020-06-15

Preparation and electrochemical performance of Si@cyclized-polyacrylonitrile/ multi-walled carbon nanotubes anode composites

1.
School of Mechantronics Engineering, Nanchang University，Nanchang 330031, China
2.
Nano Carbon Co. Ltd., Nanchang 330031, China

摘要

摘要: 通过简单高能球磨和高温热解法制备了锂离子电池Si/C电极复合材料，聚丙烯腈（PAN）包覆的纳米颗粒（Si@PAN）与多壁碳纳米管（MWCNTs）混合，制得Si@环化PAN/MWCNTs（Si@c-PAN/MWCNTs）复合材料作为锂离子电池的负极材料。包覆在纳米Si外层的高温热解后的PAN能够有效缓冲Si在充放电过程中巨大的体积变化产生的应力，同时MWCNTs作为Si@c-PAN的基体阻止Si@c-PAN颗粒的团聚，也提高了Si@c-PAN/MWCNTs复合材料电极的导电性能。电化学测试结果表明，Si@c-PAN/MWCNTs复合材料电极在电流密度为0.2 A/g时，其首次放电比容量达到2 098 mA•h/g，库伦效率达到86%；循环50次后Si@c-PAN/MWCNTs复合材料电极的可逆比容量仍能够达到1 278 mA•h/g，在2 A/g放电时其比容量为600 mA•h/g，仍保持良好的循环稳定性。
- Si /
- 聚丙烯腈 /
- 碳纳米管 /
- 锂离子电池 /
- 比容量
Abstract: Si/C electrode composites were prepared by simple high-energy ball milling and high-temperature pyrolysis. The polyacrylonitrile (PAN) coated nano Si particles (Si@PAN) were mixed with multi-walled carbon nanotubes (MWCNTs) to prepare Si@cyclized-PAN/MWCNTs(Si@c-PAN/MWCNTs) composites as the anode material for lithium ion battery. A thin layer of c-PAN was coated on Si nanoparticles to efficiently accommodate a large volume change of Si particles in cycles. The MWCNTs network functions as matrix for Si@c-PAN nano particles, which not only prevent the agglomeration of Si@c-PAN particles, but also improve the electrical conductivity of electrodes significantly. The electrochemical tests show that the first discharge specific capacity of the Si@c-PAN/MWCNTs composite electrode is 2 098 mA•h/g at the current density of 0.2 A/g and the initial coulomb efficiency is 86%. After 50 cycles, the reversible specific capacity of Si@c-PAN/MWCNTs composite electrode maintains at 1 278 mA•h/g. When the current rate reaches 2 A/g, the specific capacity of Si@c-PAN/MWCNTs composite electrode keeps at 600 mA•h/g, exhibiting good cycle stability.
- Si /
- polyacrylonitrile /
- multi-walled carbon nanotubes /
- lithium-ion battery /
- specific capacity

HTML全文

图 1 Si@环化聚丙烯腈(c-PAN)/多壁碳纳米管(MWCNTs)复合材料的制备流程

Figure 1. Preparation process of Si@cyclized-polyacrylonitrile(c-PAN)/multi-walled carbon nanotubes(MWCNTs) composites

下载: 全尺寸图片幻灯片

图 2 Si@c-PAN/MWCNTs (a)、Si@c-PAN (b)、Si/MWCNTs复合材料(c)、PAN(d)和纳米Si(e)的SEM图像

Figure 2. SEM images of Si@c-PAN/MWCNTs(a), Si@c-PAN(b), Si/MWCNTs(c), PAN(d) and nano Si(e)

下载: 全尺寸图片幻灯片

图 3 Si@c-PAN/MWCNTs复合材料的TEM图像

Figure 3. TEM images of Si@c-PAN/MWCNTs composites

下载: 全尺寸图片幻灯片

图 4 Si@c-PAN/MWCNTs、Si@c-PAN、Si/MWCNTs复合材料和Si的XRD图谱

Figure 4. XRD patterns of Si@c-PAN/MWCNTs, Si@c-PAN , Si/MWCNTs composites and Si

下载: 全尺寸图片幻灯片

图 5 三种Li-Si复合材料电池电化学性能

Figure 5. Electrochemical performance of three Li-Si composite batteries

下载: 全尺寸图片幻灯片

图 6 Si@c-PAN/MWCNT_S、Si@c-PAN和Si/MWCNT_S复合材料的倍率性能(a)和循环性能对比(b)

Figure 6. Ratio performance (a) and cycle performance (b) comparison of Si@c-PAN/MWCNT_S, Si@c-PAN and Si/MWCNT_S composites

下载: 全尺寸图片幻灯片

图 7 三种Li-Si复合材料电池放电前(a)和放电后(b)的交流阻抗(EIS)曲线

Figure 7. Electrochemical impedance spectroscopy(EIS) curves of three Li-Si composite batteries before (a) and after discharge (b)

下载: 全尺寸图片幻灯片

图 8 Si@c-PAN/MWCNTs(a)、 Si@c-PAN(b)和Si/MWCNTs复合材料电池(c)循环伏安曲线

Figure 8. CV curves of Si@c-PAN/MWCNTs (a), Si@c-PAN (b) and Si/MWCNTs composite batteries (c)

下载: 全尺寸图片幻灯片

图 9 Si@c-PAN/MWCNTs(a)、Si@c-PAN(b)和Si/MWCNTs复合材料电池(c)充放电50次后的SEM图像

Figure 9. SEM images of Si@c-PAN/ MWCNTs (a), Si@c-PAN (b) and Si/MWCNTs composite batteries (c) after 50 cycles

下载: 全尺寸图片幻灯片

参考文献(26)

[1]	SCHMUCH R, WAGNER R, GERHARD H, et al. Performance and cost of materials for lithium-based rechargeable automotive batteries[J]. Nature Energy,2018,3(4):267-278. doi: 10.1038/s41560-018-0107-2
[2]	CASIMIR A, ZHANG H, OGOKE O, et al. Silicon-based anodes for lithium-ion batteries: Effectiveness of materials synthesis and electrode preparation[J]. Nano Energy,2016,27:359-376. doi: 10.1016/j.nanoen.2016.07.023
[3]	LIANG B, LIU Y, XU Y. Silicon-based materials as high capacity anodes for next generation lithium ion batteries[J]. Journal of Power Sources,2014,267:469-490. doi: 10.1016/j.jpowsour.2014.05.096
[4]	YIN Y X, WAN L J, GUO Y G. Silicon-based nanomaterials for lithium-ion batteries[J]. Chinese Science Bulletin,2012,57(32):4104-4110. doi: 10.1007/s11434-012-5017-2
[5]	ZHOU X Y, TANG J J, YANG J, et al. Silicon@carbon hollow core-shell heterostructures novel anode materials for lithium ion batteries[J]. Electrochimica Acta,2013,87(1):663-668.
[6]	WU H, CUI Y. Designing nanostructured Si anodes for high energy lithium ion batteries[J]. Nano Today,2012,7(5):414-429. doi: 10.1016/j.nantod.2012.08.004
[7]	LIU L, LYU J, LI T, et al. Well-constructed silicon-based materials as high-performance lithium-ion battery anodes[J]. Nanoscale,2015,8(2):701-722.
[8]	LIU L, PENG J, WANG G, et al. Synthesis of mesoporous TiO2@C@MnO₂ multi-shelled hollow nanospheres with high rate capability and stability for lithium-ion batteries[J]. RSC Advances,2016,6(69):65243-65251. doi: 10.1039/C6RA14156K
[9]	REHMAN S, GUO S, HOU Y. Rational design of Si/SiO₂@hierarchical porous carbon spheres as efficient polysulfide reservoirs for high-performance Li-S battery[J]. Advanced Materials,2016,28(16):3167-3172. doi: 10.1002/adma.201506111
[10]	梁剑文. 硅纳米负极材料的化学法制备及其锂离子电池性能[D]. 合肥: 中国科学技术大学, 2015. LIANG J W. Chemical synthesis of nano-silicon materials and their lithium batteries property[D]. Hefei: University of Science and Technology of China, 2015.
[11]	LIANG J, LI X, ZHU Y, et al. Hydrothermal synthesis of nano-silicon from a silica sol and its use in lithium ion batteries[J]. Nano Research,2015,8(5):1497-1504. doi: 10.1007/s12274-014-0633-6
[12]	阮威, 王英, 唐仁衡, 等. 沥青包覆Si/G/C复合材料的制备与性能研究[J]. 电源技术, 2017, 41(4):533-536. doi: 10.3969/j.issn.1002-087X.2017.04.008 WEI R, YING W, TANG R H, et al. Study on preparation and property of pitch-coated silicon/graphite/carbon compo-site[J]. Chinese Journal of Power Sources,2017,41(4):533-536(in Chinese). doi: 10.3969/j.issn.1002-087X.2017.04.008
[13]	JU Y J, INYEONG K, KYUNG W Y, et al. Highly conducting fibrous carbon-coated silicon alloy anode for lithium ion batteries[J]. Applied Surface Science,2018,454:277-283. doi: 10.1016/j.apsusc.2018.05.165
[14]	SHI W, CHEN J, YANG Q, et al. Novel three-dimensional carbon nanotube-graphene architecture with abundant chambers and its application in lithium-silicon batteries[J]. Journal of Physical Chemistry C,2016,120(25):13807-13814. doi: 10.1021/acs.jpcc.6b03864
[15]	WON S K, JONGHYUN C, SEONG H H. Meso-porous silicon-coated carbon nanotube as an anode for lithium-ion battery[J]. Nano Research,2016,9(7):2174-2181. doi: 10.1007/s12274-016-1106-x
[16]	王海帆, 魏伟, 秦磊, 等. 碳纳米管的微观结构调节对锂空气电池电化学行为的影响[J]. 新型炭材料, 2016, 31(3):307-314. WANG H F, WEI W, QIN L, et al. Influence of the KOH activation of carbon nanotubes on their electrochemical behavior in lithium-air batteries[J]. New Carbon Materials,2016,31(3):307-314(in Chinese).
[17]	LI D, LI X, PAN Y, et al. Flexible highly specific capacitance aerogel electrodes based on cellulose nanofibers, carbon nanotubes and polyaniline[J]. Electrochimica Acta,2015,182:264-271. doi: 10.1016/j.electacta.2015.09.096
[18]	赫文秀, 于慧颖, 张永强, 等. Ni(OH)2-碳纳米管-还原氧化石墨烯复合材料的制备及电化学性能[J]. 复合材料学报, 2018, 35(7):1921-1929. HAO W X, YU H Y, ZHANG Y Q, et al. Preparation and electrochemical properties of Ni(OH)₂-carbon nanotubes-reduced graphene oxide composites[J]. Acta Materiae Compositae Sinica,2018,35(7):1921-1929(in Chinese).
[19]	LIU N, WU H, MCDOWELL M T, et al. A yolk-shell design for stabilized and scalable Li-ion battery alloy anodes[J]. Nano Letters,2012,12(6):3315-3321. doi: 10.1021/nl3014814
[20]	CETINKAYA T, UYSAL M, GULER M O, et al. Improvement cycleability of core-shell silicon/copper composite electrodes for Li-ion batteries by using electroless depo-sition of copper on silicon powders[J]. Powder Technology,2014,253(2):63-69.
[21]	JIN H U, HONG L I, HUANG X, et al. Electrochemical behavior and microstructure variation of hard carbon nano-spherules as anode material for Li-ion batteries[J]. Solid State Ionics,2007,178(3):265-271.
[22]	HANG T, MUKOYAMA D, NARA H, et al. Electrochemical impedance spectroscopy analysis for lithium-ion battery using Li₄Ti₅O₁₂ anode[J]. Journal of Power Sources,2013,222(2):442-447.
[23]	庄全超, 徐守冬, 邱祥云, 等. 锂离子电池的电化学阻抗谱分析[J]. 化学进展, 2010, 22(6):1044-1057. ZHUANG Q C, XU S D, QIU X Y, et al. Diagnosis of electrochemical impedance spectroscopy in lithium-ion batteries[J]. Progress in Chemistry,2010,22(6):1044-1057(in Chinese).
[24]	DONG X, LU C, WANG L, et al. Polyacrylonitrile-based turbostratic graphite-like carbon wrapped silicon nanoparticles: A new-type anode material for lithium ion electrode[J]. RSC Advances,2016(6):12737-12743.
[25]	ZHU B, JIN Y, TAN Y, et al. Scalable production of Si nanoparticles directly from low grade sources for lithium-ion electrode anode[J]. Nano Letters,2015,15(9):5750-5754. doi: 10.1021/acs.nanolett.5b01698
[26]	HAN W, XIAO J T, WANG C, et al. Micro-sized nano-porous Si/C anodes for lithium ion batteries[J]. Nano Energy,2015,11:490-499. doi: 10.1016/j.nanoen.2014.11.031