Ligand-channel-enabled ultrafast Li-ion conduction

Di Lu; Ruhong Li; Muhammad Mominur Rahman; Pengyun Yu; Ling Lv; Sheng Yang; Yiqiang Huang; Chuangchao Sun; Shuoqing Zhang; Haikuo Zhang; Junbo Zhang; Xuezhang Xiao; Tao Deng; Liwu Fan; Lixin Chen; Jianping Wang; Enyuan Hu; Chunsheng Wang; Xiulin Fan

doi:10.1038/s41586-024-07045-4

Ligand-channel-enabled ultrafast Li-ion conduction

Nature. 2024 Mar;627(8002):101-107. doi: 10.1038/s41586-024-07045-4. Epub 2024 Feb 28.

Authors

Di Lu^#¹, Ruhong Li^#¹, Muhammad Mominur Rahman², Pengyun Yu^{3

4}, Ling Lv¹, Sheng Yang⁵, Yiqiang Huang¹, Chuangchao Sun¹, Shuoqing Zhang¹, Haikuo Zhang¹, Junbo Zhang¹, Xuezhang Xiao¹, Tao Deng⁶, Liwu Fan⁵, Lixin Chen^{1

7}, Jianping Wang^{3

4}, Enyuan Hu⁸, Chunsheng Wang⁹, Xiulin Fan¹⁰

Affiliations

¹ State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, China.
² Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA.
³ Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
⁴ University of the Chinese Academy of Sciences, Beijing, China.
⁵ State Key Laboratory of Clean Energy Utilization, School of Energy Engineering, Zhejiang University, Hangzhou, China.
⁶ Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA.
⁷ Key Laboratory of Advanced Materials and Applications for Batteries of Zhejiang Province, Hangzhou, China.
⁸ Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA. enhu@bnl.gov.
⁹ Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA. cswang@umd.edu.
¹⁰ State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, China. xlfan@zju.edu.cn.

^# Contributed equally.

PMID: 38418886
DOI: 10.1038/s41586-024-07045-4

Abstract

Li-ion batteries (LIBs) for electric vehicles and aviation demand high energy density, fast charging and a wide operating temperature range, which are virtually impossible because they require electrolytes to simultaneously have high ionic conductivity, low solvation energy and low melting point and form an anion-derived inorganic interphase^1-5. Here we report guidelines for designing such electrolytes by using small-sized solvents with low solvation energy. The tiny solvent in the secondary solvation sheath pulls out the Li⁺ in the primary solvation sheath to form a fast ion-conduction ligand channel to enhance Li⁺ transport, while the small-sized solvent with low solvation energy also allows the anion to enter the first Li⁺ solvation shell to form an inorganic-rich interphase. The electrolyte-design concept is demonstrated by using fluoroacetonitrile (FAN) solvent. The electrolyte of 1.3 M lithium bis(fluorosulfonyl)imide (LiFSI) in FAN exhibits ultrahigh ionic conductivity of 40.3 mS cm^-1 at 25 °C and 11.9 mS cm^-1 even at -70 °C, thus enabling 4.5-V graphite||LiNi_0.8Mn_0.1Co_0.1O₂ pouch cells (1.2 Ah, 2.85 mAh cm^-2) to achieve high reversibility (0.62 Ah) when the cells are charged and discharged even at -65 °C. The electrolyte with small-sized solvents enables LIBs to simultaneously achieve high energy density, fast charging and a wide operating temperature range, which is unattainable for the current electrolyte design but is highly desired for extreme LIBs. This mechanism is generalizable and can be expanded to other metal-ion battery electrolytes.