Citation: GUO Feng, CHEN Peng, KANG Tuo, WANG Yalong, LIU Chenghao, SHEN Yanbin, LU Wei, CHEN Liwei. Silicon-loaded Lithium-Carbon Composite Microspheres as Lithium Secondary Battery Anodes[J]. Acta Physico-Chimica Sinica, ;2019, 35(12): 1365-1371. doi: 10.3866/PKU.WHXB201903008 shu

Silicon-loaded Lithium-Carbon Composite Microspheres as Lithium Secondary Battery Anodes

GUO Feng ^1,2 ,
CHEN Peng ² ,
KANG Tuo ^2,3 ,
WANG Yalong ⁴ ,
LIU Chenghao ⁴ ,
SHEN Yanbin ^1,2,, ,
LU Wei ^1,2 ,
CHEN Liwei ^1,2,5,,

1.
School of Nano Technology and Nano Bionics, University of Science and Technology of China, Hefei 230026, P. R. China
2.
i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu Province, P. R. China
3.
School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen 518055, Guangdong Province, P. R. China
4.
China Energy Lithium Co., Tianjin 300465, P. R. China
5.
School of Chemistry and Chemical Engineering, Shanghai Jiaotong University, Shanghai 200240, P. R. China

Corresponding author: SHEN Yanbin, ybshen2017@sinano.ac.cn CHEN Liwei, lwchen2008@sinano.ac.cn
Received Date: 4 March 2019
Revised Date: 2 April 2019
Accepted Date: 2 April 2019
Available Online: 10 December 2019
Fund Project: The project was supported by the National Basic Research Program of China (2016YFB0100102), the "Strategic Priority Research Program" of the CAS, China (XDA09010600, XDA09010303), and the National Nature Science Foundation of China (21625304, 21733012)the National Nature Science Foundation of China 21733012the National Basic Research Program of China 2016YFB0100102the National Nature Science Foundation of China 21625304the "Strategic Priority Research Program" of the CAS, China XDA09010600the "Strategic Priority Research Program" of the CAS, China XDA09010303

Lithium metal is the most promising anode material for Li (ion) batteries from the viewpoint of energy density because of its high theoretical specific capacity (3860 mAh∙g^-1, 2061 mAh∙cm⁻³) and low reduction potential (−3.04 V vs standard hydrogen electrode (SHE)). Lithium has been used as an anode material for lithium metal batteries since the 1970s. However because of the serious reaction between Li and non-aqueous electrolytes, the large volume expansion during Li plating, and the formation of Li dendrites during cycling, Li batteries with Li metal anodes show very low Coulombic efficiency (CE) and are easily short-circuited. This limits the widespread commercialization of Li metal anodes for Li batteries. Motivated by our previous study on the development of a Li carbon nanotube (Li-CNT) composite anode material, in this study, we prepared a Si-loaded Li carbon nanotube composite (Li-CNT-Si) via a facile molten impregnation method. The introduction of Si nanoparticles increased the Li content of the composite, thus increasing its specific capacity (the specific capacity of the Li-CNT composite increased from 2000 mAh∙g^-1 to 2600 mAh∙g^-1 with the addition of 10% Si (mass fraction)). Moreover, Si nanoparticles decreased the polarization for Li plating/stripping, resulting in an improved electrochemical performance. The Li-CNT-Si composite showed the merits of the Li-CNT composite with the advantages of limited electrode volume expansion and negligible Li dendrite formation during cycling. Furthermore, the Si nanoparticles filled the pores inside the Li-CNT microspheres, thus preventing the electrolyte from flowing into the microspheres to corrode the Li metal present inside them. Hence, the incorporation of Si nanoparticles improved the CE of the composite anode. When the 10% Si-loaded Li-CNT-Si composite was used as an anode and coupled with a commercial LiFePO₄ cathode, the resulting battery showed more than 900 stable cycles in an ether-based electrolyte at a charge/discharge rate of 1C (0.7 mA∙cm^-2) corresponding to a CE of 96.7%, which is considerably higher than those of the Li-CNT (90.1%) and Li metal foil (79.3%) anodes obtained under the same conditions. We believe that the Li-CNT-Si composite prepared in this study is a promising anode material for Li secondary batteries having high energy density, particularly for those employing Li-free cathodes, e.g., Li-sulfur and Li-oxygen batteries.
- Silicon carbon microsphere,
- Lithium carbon composite,
- Lithium metal,
- Lithium battery,
- Anode
1. [1]
  Tarascon, J. M.; Armand, M. Nature 2001, 414 (6861), 359. doi: 10.1038/35104644 doi: 10.1038/35104644
2. [2]
  Li, M.; Lu, J.; Chen, Z.; Amine, K. Adv. Mater. 2018, 1800561. doi: 10.1002/adma.201800561 doi: 10.1002/adma.201800561
3. [3]
  George, E. B. J. Electrochem Soc. 2017, 164 (1), A5019. doi: 10.1149/2.0251701jes doi: 10.1149/2.0251701jes
4. [4]
  Xu, W.; Wang, J.; Ding, F.; Chen, X.; Nasybulin, E.; Zhang, Y.; Zhang, J. Energy Environ. Sci. 2014, 7. doi: 10.1039/C3EE40795K doi: 10.1039/C3EE40795K
5. [5]
  Zhang, S. S. J. Power Sources 2013, 231 (2), 153. doi: 10.1016/j.jpowsour.2012.12.102 doi: 10.1016/j.jpowsour.2012.12.102
6. [6]
  Zhang, Y. T.; Liu, Z. J.; Wang, J. W.; Wang, L.; Peng, Z. Q. Acta Phys. -Chim. Sin. 2017, 33 (3), 486. doi: 10.3866/PKU.WHXB201611181
7. [7]
  Lin, D.; Liu, Y.; Cui, Y. Nat. Nanotechnol. 2017, 12 (3), 194. doi: 10.1038/nnano.2017.16 doi: 10.1038/nnano.2017.16
8. [8]
  Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Chem. Rev. 2017, doi: 10.1021/acs.chemrev.7b00115 doi: 10.1021/acs.chemrev.7b00115
9. [9]
  Lang, J.; Qi, L.; Luo, Y.; Wu, H. Energy Storage Mater. 2017, 7, 115. doi: 10.1016/j.ensm.2017.01.006 doi: 10.1016/j.ensm.2017.01.006
10. [10]
  Zheng, J.; Engelhard, M. H.; Mei, D.; Jiao, S.; Polzin, B. J.; Zhang, J. G.; Xu, W. Nat. Energy 2017, 2 (3), 17012. doi: 10.1038/nenergy.2017.12 doi: 10.1038/nenergy.2017.12
11. [11]
  Liu, F. Q.; Wang, W. P.; Yin, Y. X.; Zhang, S. F.; Shi, J. L.; Wang, L.; Zhang, X.; Zheng, Y.; Zhou, J.; Li, L.; et al. Sci. Adv. 2018, 4 (10), 1. doi: 10.1126/sciadv.aat5383 doi: 10.1126/sciadv.aat5383
12. [12]
  Cha, E.; Patel, M. D.; Park, J.; Hwang, J.; Prasad, V.; Cho, K.; Choi, W. Nat. Nanotechnol. 2018. doi: 10.1038/s41565-018-0061-y doi: 10.1038/s41565-018-0061-y
13. [13]
  Lopez, J; Pei, A.; Oh, J. Y.; Wang, G. J. N.; Cui, Y.; Bao, Z. N. J. Am. Chem. Soc. 2018, 140, 11735. doi: 10.1021/jacs.8b06047 doi: 10.1021/jacs.8b06047
14. [14]
  Xie, J.; Wang, J.; Lee, H. R.; Yan, K.; Li, Y.; Shi, F.; Huang, W.; Pei, A.; Chen, G.; Subbaraman, R.; et al. Sci. Adv. 2018, 4 (7), eaat5168. doi: 10.1126/sciadv.aat5168 doi: 10.1126/sciadv.aat5168
15. [15]
  Liu, K.; Kong, B.; Liu, W.; Sun Y.; Song, M. S.; Chen, J.; Liu, Y.; Lin, D.; Pei A.; Cui Y. Joule 2018, 2, 1. doi: 10.1016/j.joule.2018.06.003 doi: 10.1016/j.joule.2018.06.003
16. [16]
  Guo, Y.; Ouyang, Y.; Li, D.; Wei, Y.; Zhai, T.; Li, H. Energy Storage Mater. 2018, 2, 1. doi: 10.1016/j.ensm.2018.05.012 doi: 10.1016/j.ensm.2018.05.012
17. [17]
  Wang, Y.; Shen, Y.; Du, Z.; Zhang, X.; Wang, K.; Zhang, H.; Kang, T.; Guo, F.; Liu, C.; Wu, X.; et al. J. Mater. Chem. A 2017, 5, 23434. doi: 10.1039/C7TA08531A doi: 10.1039/C7TA08531A
18. [18]
  Guo, F.; Wang, Y.; Kang, T.; Liu, C.; Shen, Y.; Lu, W.; Wu, X.; Chen, L. Energy Storage Mater. 2018, 15, 116. doi: 10.1016/j.ensm.2018.03.018 doi: 10.1016/j.ensm.2018.03.018
19. [19]
  Shen X.; Tian Z.; Fan R.; Shao, L.; Zhang, D.; Cao, G.; Kou, L.; Bai, Y. J. Energy Chem. 2018, 27, 1067. doi: 10.1016/j.jechem.2017.12.012 doi: 10.1016/j.jechem.2017.12.012
20. [20]
  Wang, J.; Chen, Z.; Guo, Y.; Huang, R.; Wang, J. J. Inorg. Mater. 2018, 33 (3), 313. doi: 10.15541/jim20170145
21. [21]
  Li, J. Y.; Li, G.; Zhang, J.; Yin, Y. X.; Yue, F.S.; Xu, Q.; Guo, Y. G. ACS Appl. Mater. Interfaces 2019, 11, 405. doi: 10.1021/acsami.8b20213 doi: 10.1021/acsami.8b20213
22. [22]
  Yi, R.; Dai, F.; Gordin, M. L.; Chen, S.; Wang, D. H. Adv. Energy Mater. 2013, 3, 295. doi: 10.1002/aenm.201200857 doi: 10.1002/aenm.201200857
23. [23]
  Wood, K. N.; Kazyak, E.; Chadwick, A. F.; Chen, K.; Zhang, J.; Thornton, K.; Dasgupta, N. P. ACS Cent. Sci. 2016, 2 (11), 790. doi: 10.1021/acscentsci.6b00260 doi: 10.1021/acscentsci.6b00260
24. [24]
  Zhang, R.; Chen, X. R.; Chen, X.; Cheng, X.; Zhang, X.; Yan, C.; Zhang, Q. Angew. Chem. Int. Ed. 2017, 129 (27), 7764. doi: 10.1002/ange.201702099 doi: 10.1002/ange.201702099
25. [25]
  Aurbach, D. J. Power Sources 2000, 89 (2), 206. doi: 10.1016/s0378-7753(00)00431-6 doi: 10.1016/s0378-7753(00)00431-6
26. [26]
  Liu, Y.; Lin, D.; Liang, Z.; Zhao, J.; Yan, K.; Cui, Y. Nat. Commun. 2016, 7, 10992. doi: 10.1038/ncomms10992 doi: 10.1038/ncomms10992
27. [27]
  Zhao, J.; Lu, Z.; Liu, N.; Lee, H. W.; McDowell, M. T.; Cui, Y. Nat. Commun. 2014, 5, 5088. doi: 10.1038/ncomms6088 doi: 10.1038/ncomms6088
28. [28]
  Zhao, J.; Zhou, G.; Yan, K.; Xie, J.; Li, Y.; Liao, L.; Jin, Y.; Liu, K.; Hsu, P. C.; Wang, J.; et al. Nat. Nanotechnol. 2017, 12, 993. doi: 10.1038/nnano.2017.129 doi: 10.1038/nnano.2017.129
1. [1]
  Jiandong Liu , Zhijia Zhang , Mikhail Kamenskii , Filipp Volkov , Svetlana Eliseeva , Jianmin Ma . Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100011-. doi: 10.3866/PKU.WHXB202308048
2. [2]
  Bowen Yang , Rui Wang , Benjian Xin , Lili Liu , Zhiqiang Niu . C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100015-. doi: 10.3866/PKU.WHXB202310024
3. [3]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . 高性能双金属氧化物负极的理性设计及储锂特性. Acta Physico-Chimica Sinica, 2025, 41(3): 2311005-. doi: 10.3866/PKU.WHXB202311005
4. [4]
  Zhiyuan TONG , Ziyuan LI , Ke ZHANG . Three-dimensional porous collector based on Cu-Li_6.4La₃Zr_1.4Ta_0.6O₁₂ composite layer for the construction of stable lithium metal anode. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 499-508. doi: 10.11862/CJIC.20240238
5. [5]
  Zhicheng JU , Wenxuan FU , Baoyan WANG , Ao LUO , Jiangmin JIANG , Yueli SHI , Yongli CUI . MOF-derived nickel-cobalt bimetallic sulfide microspheres coated by carbon: Preparation and long cycling performance for sodium storage. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 661-674. doi: 10.11862/CJIC.20240363
6. [6]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . 钠离子电池中铁基异质结构负极材料的最新研究进展. Acta Physico-Chimica Sinica, 2025, 41(3): 2311015-. doi: 10.3866/PKU.WHXB202311015
7. [7]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
8. [8]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
9. [9]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
10. [10]
  Yang LIU , Lijun WANG , Hongyu WANG , Zhidong CHEN , Lin SUN . Surface and interface modification of porous silicon anodes in lithium-ion batteries by the introduction of heterogeneous atoms and hybrid encapsulation. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 773-785. doi: 10.11862/CJIC.20250015
11. [11]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
12. [12]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
13. [13]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
14. [14]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
15. [15]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
16. [16]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
17. [17]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
18. [18]
  Yuting ZHANG , Zunyi LIU , Ning LI , Dongqiang ZHANG , Shiling ZHAO , Yu ZHAO . Nickel vanadate anode material with high specific surface area through improved co-precipitation method: Preparation and electrochemical properties. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2163-2174. doi: 10.11862/CJIC.20240204
19. [19]
  Yueguang Chen , Wenqiang Sun . “Carbon” Adventures. University Chemistry, 2024, 39(9): 248-253. doi: 10.3866/PKU.DXHX202308074
20. [20]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(1063)
HTML views(91)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142