柱状金属锂沉积物：电解液添加剂的影响

doi:10.3866/PKU.WHXB202007058

Abstract

Abstract:

With the booming growth market of electric vehicles and portable electronics, high-energy-density rechargeable lithium ion batteries are being extensively used to advance high-end devices. Lithium-ion batteries with graphite anodes approach the ceiling in energy density, but they cannot satisfy the current demand. Among the next-generation electrodes, lithium metal anodes are strong candidates because of their high theoretical capacity and the most negative electrochemical potential. However, lithium metal batteries have been abandoned because of their poor safety resulting from the growth of lithium dendrites during lithium deposition. Although several strategies have been proposed to suppress the generation of lithium dendrites as well as the side reactions between active lithium and the electrolyte, lithium metal anodes have not been practically applied so far. Various studies have been conducted on the factors influencing lithium deposition, with the aim of understanding the growth behavior of lithium dendrites. The electrolyte plays a crucial role in the performance of the working Li metal anode. In this study, a unique battery system is proposed to realize columnar lithium deposition, which is convenient for obtaining the length and diameter of lithium deposits. The influence of different electrolytes on lithium deposition was investigated by comparing the length-diameter (L/D) ratio of the lithium deposits in two kinds of electrolytes (1.0 mol·L^-1 LiPF₆-ethylene carbonate/diethyl carbonate (EC/DEC, 1 : 1 by volume) and 1.0 mol·L^-1 LiPF₆-5% (volume fraction) fluoroethylene carbonate (FEC)-EC/DEC (1 : 1 by volume)). The morphology of the lithium deposits was strongly affected by the electrolyte composition. In the electrolyte with the FEC additive, the diameter of columnar lithium increased from 0.3-0.6 μm to 0.7-1.3 μm, while the L/D ratio decreased from 12.5 to 5.6. The small L/D ratio can reduce the reactive area between the lithium metal anode and the electrolyte, which is beneficial for achieving high lithium utilization and a long lifespan. To probe the origin of this influence, the surface chemistry of the cycled lithium metal anode was investigated by X-ray photoelectron spectroscopy. The FEC additive can increase the proportion of lithium fluoride (LiF) in the solid electrolyte interphase, which is conducive for the rapid diffusion of lithium ions. As a result, fewer nucleation sites are formed, providing more space for the growth of lithium cores with a large diameter. Therefore, the addition of FEC leads to a decrease in the L/D ratio of columnar lithium.

Key words: Lithium metal battery, Columnar lithium, Electrolyte, Lithium fluoride, Length-diameter ratio

Shijie Yang, Xiangqun Xu, Xinbing Cheng, Xinmeng Wang, Jinxiu Chen, Ye Xiao, Hong Yuan, He Liu, Aibing Chen, Wancheng Zhu, Jiaqi Huang, Qiang Zhang. Columnar Lithium Metal Deposits: the Role of Non-Aqueous Electrolyte Additive[J].Acta Phys. -Chim. Sin., 2021, 37(1): 2007058.

Figures/Tables 7

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Reagent	Parameters	Company
Li mental	Thickness: 50, 600 μm	China Energy Lithium Co., Ltd. Aladdin
Cu	Thickness: 9 μm	China Energy Lithium Co., Ltd. Aladdin
CH₃CH₂OH	99.8%	Beijing Chemical Plant Co. LTD
CH₃COCH₃	99.8%	Beijing Chemical Plant Co. LTD
1 mol∙L⁻¹ LiPF₆-ethylene carbonate : diethyl carbonate (1 : 1 by volume)	99.8%	DoDoChem
Fluoroethylene carbonate	99.8%	DoDoChem
KAPTON tape	–	E. I. Du Pont Company
HCl	36.5%	Beijing Chemical Plant Co. LTD

Electrolyte	Diameter distribution/μm	Length distribution/μm	L/D ratio ^a
No FEC	0.3–0.6	4.5–5.5	12.5
5% FEC	0.7–1.3	4.9–5.9	5.6

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Columnar Lithium Metal Deposits: the Role of Non-Aqueous Electrolyte Additive

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