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]
  Zhiming Cui , Yuanlong Wu . 综合创新实验：基于原位聚合技术的固态锂金属电池的构筑及性能评价. University Chemistry, 2026, 41(9): 313-323. doi: 10.12461/PKU.DXHX202508043
2. [2]
  Xue Xiao , Jiachun Li , Xiangtong Meng , Jieshan Qiu . Sulfur-Doped Carbon-Coated Fe_0.95S_1.05 Nanospheres as Anodes for High-Performance Sodium Storage. Acta Physico-Chimica Sinica, 2024, 40(6): 2307006-0. doi: 10.3866/PKU.WHXB202307006
3. [3]
  Fan Yang , Zheng Liu , Da Wang , KwunNam Hui , Yelong Zhang , Zhangquan Peng . Preparation and Properties of P-Bi₂Te₃/MXene Superstructure-based Anode for Potassium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2303006-0. doi: 10.3866/PKU.WHXB202303006
4. [4]
  Xuechen Hu , Qiuying Xia , Fan Yue , Xinyi He , Zhenghao Mei , Jinshi Wang , Hui Xia , Xiaodong Huang . Electrochemical Characteristics of LiNbO₃ Anode Film and Its Applications in All-Solid-State Thin-Film Lithium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2309046-0. doi: 10.3866/PKU.WHXB202309046
5. [5]
  Jiandong Liu , Zhijia Zhang , Kamenskii Mikhail , Volkov Filipp , Eliseeva Svetlana , Jianmin Ma . Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100011-0. doi: 10.3866/PKU.WHXB202308048
6. [6]
  Jingyi Zhang , Tianyue Gao , Xiaoqing Qiu . A journey through time: the legend of lithium-ion batteries. University Chemistry, 2026, 41(4): 337-342. doi: 10.12461/PKU.DXHX202502100
7. [7]
  Hengrui Zhang , Xijun Xu , Xun-Lu Li , Xiangwen Gao . Applications of Generative Artificial Intelligence in Battery Research: Current Status and Prospects. Acta Physico-Chimica Sinica, 2025, 41(10): 100115-0. doi: 10.1016/j.actphy.2025.100115
8. [8]
  Zeyu Liu , Wenze Huang , Yang Xiao , Jundong Zhang , Weijin Kong , Peng Wu , Chenzi Zhao , Aibing Chen , Qiang Zhang . Nanocomposite Current Collectors for Anode-Free All-Solid-State Lithium Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2305040-0. doi: 10.3866/PKU.WHXB202305040
9. [9]
  Keke Gao , Haozhe Xu , Xingkun Liu , Chunwen Sun . Cr-doped lithium-rich manganese-based materials as a cathode for high-performance all-solid-state lithium batteries. Acta Physico-Chimica Sinica, 2026, 42(3): 100200-0. doi: 10.1016/j.actphy.2025.100200
10. [10]
  Tao Xu , Wei Sun , Tianci Kong , Jie Zhou , Yitai Qian . Stable Graphite Interface for Potassium Ion Battery Achieving Ultralong Cycling Performance. Acta Physico-Chimica Sinica, 2024, 40(2): 2303021-0. doi: 10.3866/PKU.WHXB202303021
11. [11]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . Rational Design of Bimetallic Oxide Anodes for Superior Li⁺ Storage. Acta Physico-Chimica Sinica, 2025, 41(3): 100021-0. doi: 10.3866/PKU.WHXB202311005
12. [12]
  Leyu DING , Ying HE , Zhihe WEI , Yang PENG , Zhao DENG . Conductive polypyrrole-confined Co-MOF-74 for high-performance lithium metal anodes. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2491-2502. doi: 10.11862/CJIC.20250176
13. [13]
  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): 100015-0. doi: 10.3866/PKU.WHXB202310024
14. [14]
  Caiyun Jin , Zexuan Wu , Guopeng Li , Zhan Luo , Nian-Wu Li . Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries. Acta Physico-Chimica Sinica, 2025, 41(8): 100094-0. doi: 10.1016/j.actphy.2025.100094
15. [15]
  Qiuxiang FANG , Xinyue CHEN , Yuyang GUO , Penghui XIE , Pengbiao GENG . Application of metal-organic framework derived materials in lithium-sulfur battery separators. Chinese Journal of Inorganic Chemistry, 2026, 42(9): 1910-1932. doi: 10.11862/CJIC.20260188
16. [16]
  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
17. [17]
  Qu ZHANG , Tao WANG , Yinying WANG , Bo LI , Dongling WU . Synthesis of amino acid-functionalized nitrogen-doped carbon dots/cuprous oxidecomposite material and its performance in aqueous zinc-ion batteries. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 488-498. doi: 10.11862/CJIC.20250272
18. [18]
  Zhang Xue , He Zihan , Wu Yingqi , Yu Weilai , Liu Tao . Corn-distillers-derived hard carbon: a sustainable high-rate, long-life anode for sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(5): 100199-. doi: 10.1016/j.actphy.2025.100199
19. [19]
  Baoshun Zhu , Xinyan Wang , Weipeng Mu , Xuanpeng Sun , Yubo Wang , Hongyu Wei , Pangyu Shi , Huilan Hao , Dashuang Wang , Guomin Li , Guizhen Wang . 回收造纸污泥制备低成本Ni改性碳/硅复合材料用于高效微波吸收. Acta Physico-Chimica Sinica, 2026, 42(11): 100417-. doi: 10.1016/j.actphy.2026.100417
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(2267)
HTML views(140)

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