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Vol. 15 (2023)

Demystifying the Salt-Induced Li Loss: A Universal Procedure for the Electrolyte Design of Lithium-Metal Batteries

https://doi.org/10.1007/s40820-023-01205-3
Zhenglu Zhu
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Xiaohui Li
Institute of Nanoscience and Nanotechnology, School of Physical Science and Technology, Central China Normal University, Wuhan 430079, People’s Republic of China
Xiaoqun Qi
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Jie Ji
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Yongsheng Ji
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Ruining Jiang
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Chaofan Liang
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Dan Yang
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Ze Yang
Institute of Nanoscience and Nanotechnology, School of Physical Science and Technology, Central China Normal University, Wuhan 430079, People’s Republic of China
Long Qie
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Yunhui Huang
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China

Corresponding Author: Long Qie

qie@hust.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 234

Abstract

Lithium (Li) metal electrodes show significantly different reversibility in the electrolytes with different salts. However, the understanding on how the salts impact on the Li loss remains unclear. Herein, using the electrolytes with different salts (e.g., lithium hexafluorophosphate (LiPF6), lithium difluoro(oxalato)borate (LiDFOB), and lithium bis(fluorosulfonyl)amide (LiFSI)) as examples, we decouple the irreversible Li loss (SEI Li+ and “dead” Li) during cycling. It is found that the accumulation of both SEI Li+ and “dead” Li may be responsible to the irreversible Li loss for the Li metal in the electrolyte with LiPF6 salt. While for the electrolytes with LiDFOB and LiFSI salts, the accumulation of “dead” Li predominates the Li loss. We also demonstrate that lithium nitrate and fluoroethylene carbonate additives could, respectively, function as the “dead” Li and SEI Li+ inhibitors. Inspired by the above understandings, we propose a universal procedure for the electrolyte design of Li metal batteries (LMBs): (i) decouple and find the main reason for the irreversible Li loss; (ii) add the corresponding electrolyte additive. With such a Li-loss-targeted strategy, the Li reversibility was significantly enhanced in the electrolytes with 1,2-dimethoxyethane, triethyl phosphate, and tetrahydrofuran solvents. Our strategy may broaden the scope of electrolyte design toward practical LMBs.


Highlights:
1 The loss mechanisms of irreversible Li in electrolytes with various salts (e.g., lithium hexafluorophosphate (LiPF6), lithium difluoro(oxalato)borate (LiDFOB), and lithium bis(fluorosulfonyl)amide (LiFSI)) are systemically revealed.
2 A universal procedure for the electrolyte design of Li metal batteries is proposed: (i) decouple and find the main reason for the irreversible Li loss; (ii) add the corresponding electrolyte additive.

Keywords

Li loss Universal guideline Electrolyte design Li reversibility
Zhu, Zhenglu, Xiaohui Li, Xiaoqun Qi, Jie Ji, Yongsheng Ji, Ruining Jiang, Chaofan Liang, Dan Yang, Ze Yang, Long Qie, and Yunhui Huang. 2023. “Demystifying the Salt-Induced Li Loss: A Universal Procedure for the Electrolyte Design of Lithium-Metal Batteries”. Nano-Micro Letters 15 (October):234. https://doi.org/10.1007/s40820-023-01205-3.
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