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Research Article | Open Access

Dual Additives for Stabilizing Li Deposition and SEI Formation in Anode-Free Li-Metal Batteries

Baolin Wu^{¹^,²}, Chunguang Chen^{³^,⁴}(), Dmitri L. Danilov^{¹^,⁵}(), Zhiqiang Chen^⁵, Ming Jiang^⁶, Rüdiger-A. Eichel^{¹^,²}, Peter H. L. Notten^{¹^,⁵^,⁷}

()

1

Forschungszentrum Jülich (IEK-9), D-52425, Jülich Germany

2

RWTH Aachen University, D-52074, Aachen Germany

3

LNM, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, China

4

School of Engineering Sciences, University of Chinese Academy of Sciences, Beijing 100049, China

5

Eindhoven University of Technology, P.O. Box 513 5600 MB, Eindhoven The Netherlands

6

School of Electronics and Information, Institute of Carbon Neutrality and New Energy, Hangzhou Dianzi University, Hangzhou 310018, China

7

University of Technology Sydney, Broadway, Sydney NSW 2007, Australia

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Abstract

Anode-free Li-metal batteries are of significant interest to energy storage industries due to their intrinsically high energy. However, the accumulative Li dendrites and dead Li continuously consume active Li during cycling. That results in a short lifetime and low Coulombic efficiency of anode-free Li-metal batteries. Introducing effective electrolyte additives can improve the Li deposition homogeneity and solid electrolyte interphase (SEI) stability for anode-free Li-metal batteries. Herein, we reveal that introducing dual additives, composed of LiAsF₆ and fluoroethylene carbonate, into a low-cost commercial carbonate electrolyte will boost the cycle life and average Coulombic efficiency of NMC||Cu anode-free Li-metal batteries. The NMC||Cu anode-free Li-metal batteries with the dual additives exhibit a capacity retention of about 75% after 50 cycles, much higher than those with bare electrolytes (35%). The average Coulombic efficiency of the NMC||Cu anode-free Li-metal batteries with additives can maintain 98.3% over 100 cycles. In contrast, the average Coulombic efficiency without additives rapidly decline to 97% after only 50 cycles. In situ Raman measurements reveal that the prepared dual additives facilitate denser and smoother Li morphology during Li deposition. The dual additives significantly suppress the Li dendrite growth, enabling stable SEI formation on anode and cathode surfaces. Our results provide a broad view of developing low-cost and high-effective functional electrolytes for high-energy and long-life anode-free Li-metal batteries.

Keywords

anode-free lithium metal battery dual additives in situ Raman Li growth SEI formation

Electronic Supplementary Material

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Energy & Environmental Materials

Volume 7 Issue 3,
May 2024

Article number: e12642

DOI: 10.1002/eem2.12642

Cite this article:

Wu B, Chen C, Danilov DL, et al. Dual Additives for Stabilizing Li Deposition and SEI Formation in Anode-Free Li-Metal Batteries. Energy & Environmental Materials, 2024, 7(3): e12642. https://doi.org/10.1002/eem2.12642

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