Issue

Vol. 16 (2024)

Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries

https://doi.org/10.1007/s40820-024-01364-x
Zejun Sun
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Jinlin Yang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Hongfei Xu
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Chonglai Jiang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Yuxiang Niu
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Xu Lian
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Yuan Liu
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Ruiqi Su
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Dayu Liu
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Yu Long
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Meng Wang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Jingyu Mao
Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore
Haotian Yang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Baihua Cui
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Yukun Xiao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Ganwen Chen
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Qi Zhang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Zhenxiang Xing
Agency for Science, Technology, and Research (A*STAR), Institute of Materials Research and Engineering, Innovis, 2 Fusionopolis Way, #08‑03, Singapore 138634, Singapore
Jisheng Pan
Agency for Science, Technology, and Research (A*STAR), Institute of Materials Research and Engineering, Innovis, 2 Fusionopolis Way, #08‑03, Singapore 138634, Singapore
Gang Wu
Agency for Science, Technology and Research (A*STAR), Institute of High-Performance Computing, 1 Fusionopolis Way, #16‑16 Connexis, Singapore 138632, Singapore
Wei Chen
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore

Corresponding Author: Wei Chen

phycw@nus.edu.sg

Nano-Micro Letters, Vol. 16 (2024), Article Number: 141

Abstract

An anion-rich electric double layer (EDL) region is favorable for fabricating an inorganic-rich solid–electrolyte interphase (SEI) towards stable lithium metal anode in ester electrolyte. Herein, cetyltrimethylammonium bromide (CTAB), a cationic surfactant, is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating. In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO3−/FSI− anions in the EDL region due to the positively charged CTA+. In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI, which helps improve the kinetics of Li+ transfer, lower the charge transfer activation energy, and homogenize Li deposition. As a result, the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm−2 with a capacity of 1 mAh cm−2. Moreover, Li||LiFePO4 and Li||LiCoO2 with a high cathode mass loading of > 10 mg cm−2 can be stably cycled over 180 cycles.


Highlights:
1 Cetyltrimethylammonium cations can shield the repelling force on anions to attract more anions into electric double layer region during lithium plating process, facilitating the formation of inorganic-rich solid-state electrolyte interphase (SEI).
2 An inorganic-rich (N/F-containing species) structure of SEI can be evidenced by the in-depth analysis.
3 The cycling lifetime of Li||Li symmetric cell in the designed electrolyte can be extended from 500 to 1300 h. Moreover, full cells with a high cathode mass loading of >10 mg cm-2 can be stably cycled over 180 cycles.

Keywords

Cationic surfactant Lithium nitrate additive Solid–electrolyte interphase Electric double layer Lithium metal batteries
Sun, Zejun, Jinlin Yang, Hongfei Xu, Chonglai Jiang, Yuxiang Niu, Xu Lian, Yuan Liu, Ruiqi Su, Dayu Liu, Yu Long, Meng Wang, Jingyu Mao, Haotian Yang, Baihua Cui, Yukun Xiao, Ganwen Chen, Qi Zhang, Zhenxiang Xing, Jisheng Pan, Gang Wu, and Wei Chen. 2024. “Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries”. Nano-Micro Letters 16 (March):141. https://doi.org/10.1007/s40820-024-01364-x.
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