物理化学学报 >> 2021, Vol. 37 >> Issue (2): 2008092.doi: 10.3866/PKU.WHXB202008073

所属专题: 金属锂负极

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稳定锂电化学沉积和溶解行为的LiC6异质微结构界面层

张自博1,2, 邓伟1, 周旭峰1,2,*(), 刘兆平1,2,*()   

  1. 1 中国科学院宁波材料技术与工程研究所,动力锂电池工程实验室,中国科学院石墨烯工程实验室,浙江省石墨烯应用研究重点实验室,浙江 宁波 315201
    2 中国科学院大学材料科学与光电技术学院,北京 100049
  • 收稿日期:2020-08-25 录用日期:2020-10-06 发布日期:2020-10-22
  • 通讯作者: 周旭峰,刘兆平 E-mail:zhouxf@nimte.ac.cn;liuzp@nimte.ac.cn

LiC6 Heterogeneous Interface for Stable Lithium Plating and Stripping

Zibo Zhang1,2, Wei Deng1, Xufeng Zhou1,2,*(), Zhaoping Liu1,2,*()   

  1. 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
  • Received:2020-08-25 Accepted:2020-10-06 Published:2020-10-22
  • Contact: Xufeng Zhou,Zhaoping Liu E-mail:zhouxf@nimte.ac.cn;liuzp@nimte.ac.cn
  • About author:Zhaoping Liu, Email: liuzp@nimte.ac.cn (Z.L.)
    Xufeng Zhou, Email: zhouxf@nimte.ac.cn (X.Z.)

摘要:

本文采用机械辊压方法在金属锂表面通过原位固相反应生成LiC6异质微结构界面层,并研究了在碳酸酯有机电解液体系下该异质层对锂电化学沉积和溶解行为的影响。通过形貌表征与电化学测试发现,LiC6异质层能够有效提升锂电化学沉积的可逆性与均匀性,从而抑制枝晶生长及维持沉积/溶解界面的稳定。使用异质层改性金属锂负极的扣式全电池也较纯金属锂负极体系表现出更为优异的循环稳定性。

关键词: 锂金属二次电池, 金属锂负极, 枝晶, 异质微结构, LiC6

Abstract:

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.

Key words: Lithium metal secondary battery, Lithium metal anode, Dendrite, Heterogeneous interface, LiC6

MSC2000: 

  • O646