Citation: Zhang Zibo, Deng Wei, Zhou Xufeng, Liu Zhaoping. LiC₆ Heterogeneous Interface for Stable Lithium Plating and Stripping[J]. Acta Physico-Chimica Sinica, ;2021, 37(2): 200809. doi: 10.3866/PKU.WHXB202008073 shu

LiC₆ Heterogeneous Interface for Stable Lithium Plating and Stripping

Zhang Zibo ^1,2 ,
Deng Wei ¹ ,
Zhou Xufeng ^1,2,, ,
Liu Zhaoping ^1,2,,

1.
Advanced Li-ion Battery Engineering Laboratory, CAS Engineering Laboratory for Graphene, Key Laboratory of Graphene Technologies and Applications of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering (NIMTE), Chinese Academy of Sciences, Ningbo 315201, Zhejiang Province, China
2.
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Zhou Xufeng, zhouxf@nimte.ac.cn Liu Zhaoping, liuzp@nimte.ac.cn
Received Date: 25 August 2020
Revised Date: 27 September 2020
Accepted Date: 6 October 2020
Available Online: 22 October 2020

Lithium metal has the highest theoretical specific energy density (3860 mAh∙g⁻¹) and the most negative redox potential (−3.04 V vs standard hydrogen electrode) among all alkali metals. These features have attracted the interest of battery researchers to put lithium metal into practical use in rechargeable batteries. However, lithium metal tends to deposit as dendritic or mossy morphology during the charging process, and such non-uniform deposition induces low Coulombic efficiency and poor cycling stability. In addition, dendritic metallic lithium can easily penetrate the separator, which causes internal short circuit and leads to severe safety issues. Thus it is important to control the electrodeposition process of lithium to inhibit the formation of Li dendrites. Surface modification of lithium is a widely adopted strategy that can induce uniform deposition of Li. In this paper, a LiC₆ heterogeneous interfacial layer is decorated on the surface of lithium metal anode. It is prepared in a simple manner by mechanically rolling graphitized carbon nanospheres on a Li foil. The increase in surface area by this LiC₆ layer can homogenize the current density on the surface of the lithium foil. Simultaneously, the electronegativity of LiC₆ can also homogenize the lithium ion flux. The effect of heterogeneous interface on the electrochemical plating and stripping behavior of lithium in carbonate electrolyte is also studied. Morphological characterization and electrochemical performance tests reveal that the LiC₆ heterogeneous interface can significantly improve the reversibility and uniformity of the electrochemical plating and stripping of Li, thereby inhibiting dendritic growth and maintaining the stability of the anode/electrolyte interface. Alternating current electrochemical impedance spectroscopy analysis determines that the solid electrolyte interface (SEI) impedance of bare lithium decreases from the initial 275 to 100 Ω as the deposition capacity increases, suggesting that severe rupture of the SEI is caused by the huge volume change after lithium deposition. On the contrary, the SEI impedance of the lithium foil with the LiC₆ heterogeneous interface layer remains nearly constant (from the initial 26 to 25 Ω after electrodeposition) indicates that the LiC₆ layer is able to inhibit dendrite growth and stabilize the interface. Thus, stable lithium plating/stripping over 300 h is achieved at a current density of 1 mA∙cm⁻² and at a fixed capacity of 1 mAh∙cm⁻² with a voltage hysteresis of less than 50 mV. The Li-LiFePO₄ full cell test demonstrates that the cycling stability of the modified lithium metal anode is superior to that of the bare one.
- Lithium metal secondary battery,
- Lithium metal anode,
- Dendrite,
- Heterogeneous interface,
- LiC₆
1. [1]
  Liu, C.; Jin, Z.; Wang, C.; Liu, H.; Zhang, Q. Energy Chem. 2019, 1 (1), 100003. doi: 10.1016/j.enchem.2019.100003 doi: 10.1016/j.enchem.2019.100003
2. [2]
  Peng, Z.; Song, J.; Huai, L.; Jia, H.; Xiao, B.; Zou, L. Adv. Energy Mater. 2019, 9 (42), 1901764. doi: 10.1002/aenm.201901764 doi: 10.1002/aenm.201901764
3. [3]
  Wang, D.; Luan, C.; Zhang, W.; Liu, X.; Wang, P.; Zheng, W. Adv. Energy Mater. 2018, 8 (21), 1800650. doi: 10.1002/aenm.201800650 doi: 10.1002/aenm.201800650
4. [4]
  Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Chem. Rev. 2017, 117 (15), 10403. doi: 10.1021/acs.chemrev.7b00115 doi: 10.1021/acs.chemrev.7b00115
5. [5]
  Yan, C.; Cheng, X. B.; Yao, Y. X.; Shen, X.; Li, B. Q.; Li, W. J.; Zhang, Q. Adv. Mater. 2018, 30(45), 1804461. doi: 10.1002/adma.201804461 doi: 10.1002/adma.201804461
6. [6]
  Xu, S. M.; Duan, H.; Shi, J. L.; Zuo, T. T.; Hu, X. C.; Lang, S. Y.; Zhang, X. Nano Res. 2020, 13 (2), 430. doi: 10.1007/s12274-020-2628-z doi: 10.1007/s12274-020-2628-z
7. [7]
  Li, N. W.; Yin, Y. X.; Yang, C. P.; Guo, Y. G. Adv. Mater. 2016, 28 (9), 1853. doi: 10.1002/adma.201504526 doi: 10.1002/adma.201504526
8. [8]
  Aurbach, D.; Gofer, Y.; Langzam, J. J. Electrochem. Soc 1989, 136, 11. doi: 10.1149/1.2096425 doi: 10.1149/1.2096425
9. [9]
  Gu, Y.; Wang, W. W.; Li, Y. J.; Wu, Q. H.; Tang, S.; Yan, J. W.; Chen, Z. B. Nat. Commun. 2018, 9 (1), 1. doi: 10.1038/s41467-018-03466-8 doi: 10.1038/s41467-018-03466-8
10. [10]
  Lee, J. I.; Shin, M.; Hong, D. Adv. Energy Mater. 2019, 9 (13), 1803722.1. doi: 10.1002/aenm.201803722 doi: 10.1002/aenm.201803722
11. [11]
  Lee, D.; Sun, S.; Kwon, J. Adv. Mater. 2020, 32, 1905573. doi: 10.1002/adma.201905573 doi: 10.1002/adma.201905573
12. [12]
  Guo, F.; Wu, C.; Chen, S. ACS. Mater. Lett. 2020, 2 (4), 358. doi: 10.1021/acsmaterialslett.0c00001 doi: 10.1021/acsmaterialslett.0c00001
13. [13]
  Guo, F.; Chen, P.; Kang, T.; Wang, Y. L.; Liu, C. H.; Shen, Y. B.; Lu, W.; Chen, L. W. Acta Phys. -Chim. Sin. 2019, 35 (12), 1365. doi: 10.3866/PKU.WHXB201903008
14. [14]
  Guo, F.; Wang, Y.; Kang, T.; Liu, C.; Shen, Y.; Lu, W.; Chen, L. Energy Storage Mater. 2018, 15, 116. doi: 10.1016/j.ensm.2018.03.018 doi: 10.1016/j.ensm.2018.03.018
15. [15]
  Shi, P.; Li, T.; Zhang, R.; Shen, X.; Huang, J.; Cheng, X.; Zhang, Q. Adv. Mater. 2019, 31(8), 1807131. doi: 10.1002/adma.201807131 doi: 10.1002/adma.201807131
16. [16]
  Cui, J.; Yao, S.; Wu, J.; Kim, J. Adv. Energy Mater. 2019, 9, 1802777. doi: 10.1002/aenm.201802777 doi: 10.1002/aenm.201802777
17. [17]
  Zhao, Q.; Liu, X.; Stalin, S.; Khan, K.; Archer, L. A. Nat Energy. 2019, 4 (5), 365. doi: 10.1038/s41560-019-0349-7 doi: 10.1038/s41560-019-0349-7
18. [18]
  Yan, K.; Lee, H. W.; Gao, T.; Zheng, G.; Yao, H.; Wang, H.; Chu, S. Nano Lett. 2014, 14(10), 6016. doi: 10.1021/nl503125u doi: 10.1021/nl503125u
19. [19]
  Kim, M. S.; Ryu, J. H.; Lim, Y. R.; Nah, I. W.; Lee, K. R.; Archer, L. A.; Cho, W. I. Nat Energy. 2018, 3 (10), 889. doi: 10.1038/s41560-018-0237-6 doi: 10.1038/s41560-018-0237-6
20. [20]
  Lin, D.; Liu, Y.; Liang, Z.; Lee, H. W.; Sun, J.; Wang, H.; Cui, Y. Nat. Nanotechnol. 2016, 11 (7), 626. doi: 10.1038/NNANO.2016.32 doi: 10.1038/NNANO.2016.32
21. [21]
  Huang, S.; Tang, L.; Najafabadi, H. S.; Chen, S.; Ren, Z. Nano Energy 2017, 38, 504. doi: 10.1016/j.nanoen.2017.06.030 doi: 10.1016/j.nanoen.2017.06.030
22. [22]
  Zhang, R.; Chen, X. R.; Chen, X.; Cheng, X. B.; Zhang, X. Q.; Yan, C.; Zhang, Q. Angew. Chem. Int. Ed. 2017, 56 (27), 7764. doi: 10.1002/anie.201702099 doi: 10.1002/anie.201702099
23. [23]
  Shao, Y.; Wang, H.; Gong, Z.; Wang, D.; Zheng, B.; Zhu, J.; Huang, X. ACS Energy Lett. 2018, 3 (6), 1212. doi: 10.1021/acsenergylett.8b00453 doi: 10.1021/acsenergylett.8b00453
24. [24]
  Siroma, Z.; Sato, T.; Tamonari, T.; Nagai, R.; Ota, A.; Ioroi, T. J. Power Sources 2016, 316, 215. doi: 10.1016/j.jpowsour.2016.03.059 doi: 10.1016/j.jpowsour.2016.03.059
25. [25]
  Salvatierra, R. V.; Yoon, J.; Tour, J. M. Adv. Mater. 2018, 30 (50), 1803869. doi: 10.1002/adma.201803869 doi: 10.1002/adma.201803869
26. [26]
  Zhou, W. F. Electrochemical measurements. Shanghai Science and Technology Press: Shanghai, 1983; pp. 134-136.
1. [1]
  .
  南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积
  . CCS Chemistry, 2025, 7(0): -.
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  Xinyu Miao , Hao Yang , Jie He , Jing Wang , Zhiliang Jin . 调整Keggin型多金属氧酸盐电子结构构建S型异质结用于光催化析氢. Acta Physico-Chimica Sinica, 2025, 41(6): 100051-. doi: 10.1016/j.actphy.2025.100051
7. [7]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
8. [8]
  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
9. [9]
  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
10. [10]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
11. [11]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
12. [12]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
13. [13]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
14. [14]
  Jingzhuo Tian , Chaohong Guan , Haobin Hu , Enzhou Liu , Dongyuan Yang . 废塑料促进S型NiCr₂O₄/孪晶Cd_0.5Zn_0.5S同质异质结光催化产氢. Acta Physico-Chimica Sinica, 2025, 41(6): 100068-. doi: 10.1016/j.actphy.2025.100068
15. [15]
  Yinyin Qian , Rui Xu . Utilizing VESTA Software in the Context of Material Chemistry: Analyzing Twin Crystal Nanostructures in Indium Antimonide. University Chemistry, 2024, 39(3): 103-107. doi: 10.3866/PKU.DXHX202307051
16. [16]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
17. [17]
  Ran HUO , Zhaohui ZHANG , Xi SU , Long CHEN . Research progress on multivariate two dimensional conjugated metal organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2063-2074. doi: 10.11862/CJIC.20240195
18. [18]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(904)
HTML views(225)

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

LiC6 Heterogeneous Interface for Stable Lithium Plating and Stripping

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

Metrics

通讯作者: 陈斌, bchen63@163.com

LiC₆ Heterogeneous Interface for Stable Lithium Plating and Stripping