Citation: Liu Ya, Zheng Lei, Gu Wei, Shen Yanbin, Chen Liwei. Surface Passivation of Lithium Metal via In situ Polymerization[J]. Acta Physico-Chimica Sinica, ;2021, 37(1): 200405. doi: 10.3866/PKU.WHXB202004058 shu

Surface Passivation of Lithium Metal via In situ Polymerization

Liu Ya ^1,2 ,
Zheng Lei ^2,3 ,
Gu Wei ^2,4 ,
Shen Yanbin ^2,, ,
Chen Liwei ^2,5,,

1.
Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, Jiangsu Province, China
2.
i-Lab, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu Province, China
3.
School of Nano Technology and Nano Bionics, University of Science and Technology of China, Hefei 230026, China
4.
School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China
5.
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Corresponding author: Shen Yanbin, ybshen2017@sinano.ac.cn Chen Liwei, lwchen2008@sinano.ac.cn
Received Date: 21 April 2020
Revised Date: 14 May 2020
Accepted Date: 14 May 2020
Available Online: 20 May 2020
Fund Project: the National Natural Science Foundation of China 21733012the Ministry of Science and Technology of China 2016YFB0100102The project was supported by the National Natural Science Foundation of China (21625304, 21733012, and 21772190) and the Ministry of Science and Technology of China (2016YFB0100102)the National Natural Science Foundation of China 21772190the National Natural Science Foundation of China 21625304

Lithium (Li) metal is considered a promising anode material for high energy density secondary Li metal batteries because it has the highest specific energy (3860 mAh·g^-1) and lowest redox potential (-3.04 V compared to standard hydrogen electrodes. However, the development of high-performance Li metal batteries is challenging. Firstly, Li dendrites tend to grow on the surface of Li metal foil, leading to a limited anodic coulombic efficiency (CE), poor cyclability, and even explosion hazards when an internal cell short circuit occurs. Moreover, Li metal suffers from serious surface stability problems and is easily corroded by electrolytes during cycling, further resulting in low CE, thus shortening the life cycle. We have developed a Li-carbon nanotube (Li-CNT) composite microsphere via a facile molten impregnation method. The Li-CNT composite's CNT framework can suppress volume changes during the charge/discharge process and help stabilize the solid electrolyte interphase (SEI), which is typically mechanically fragile. As a result, Li-CNT shows a high specific capacity (2000 mAh·g^-1) and can significantly suppress dendrite formation by reducing the current density, resulting in enhanced safety and cycling stability. However, the large specific surface area of the Li-CNT microspheres also enables increased reaction with the air and the electrolyte. A passivation layer is critical for the practical application of Li-CNT during the electrochemical cycling and manufacturing process. LiF is an important component of SEI in the liquid electrolyte system, and a uniform and dense LiF-rich SEI film can enable stable cycling. Moreover, LiF has been widely used as the preferred coating material to protect Li metal anodes through different methods. In this study, we improved the Li-CNT composite stability by constructing a uniform LiF-rich protecting layer on the surface through in situ polymerization of 4-fluorostyrene. The F functional group of 4-fluorostyrene, which is a lithiophilic group, reacts with the Li-CNT to produce a uniform LiF-rich layer on the surface of the Li-CNT via a facile and scalable liquid-phase reaction. The resulting passivation layer effectively suppresses the Li-CNT corrosion by the electrolyte and air, leading to better environmental and electrochemical stability. Consequently, after exposure to dry-air with a dew point -40 ℃ for 24 h, the specific capacity of the surface passivated Li-CNT is still as high as 1129 mAh·g^-1, corresponding to a capacity retention of 52.85%. When the surface passivated Li-CNT is paired with a LiFePO₄ cathode (the capacity ratio of cathode and anode is 1 : 6), a prolonged lifespan of over 280 cycles at 0.5C was reached, corresponding to a CE of 97.7%. The in situ polymerization passivation is simple and easy to be scale up; thus, it is a promising method for developing Li metal anodes towards the practical Li metal batteries.
- Li-carbon nanotube,
- Li metal battery,
- LiF,
- In situ polymerization,
- Li dendrite
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