Revealing the Multifunctions of Li3N in the Suspension Electrolyte for Lithium Metal Batteries

Mun Sek Kim; Zewen Zhang; Jingyang Wang; Solomon T Oyakhire; Sang Cheol Kim; Zhiao Yu; Yuelang Chen; David T Boyle; Yusheng Ye; Zhuojun Huang; Wenbo Zhang; Rong Xu; Philaphon Sayavong; Stacey F Bent; Jian Qin; Zhenan Bao; Yi Cui

doi:10.1021/acsnano.2c12470

Revealing the Multifunctions of Li₃N in the Suspension Electrolyte for Lithium Metal Batteries

ACS Nano. 2023 Feb 14;17(3):3168-3180. doi: 10.1021/acsnano.2c12470. Epub 2023 Jan 26.

Authors

Mun Sek Kim^{1

2}, Zewen Zhang¹, Jingyang Wang^{1

3}, Solomon T Oyakhire², Sang Cheol Kim¹, Zhiao Yu^{2

4}, Yuelang Chen^{2

4}, David T Boyle^{1

4}, Yusheng Ye¹, Zhuojun Huang^{1

2}, Wenbo Zhang¹, Rong Xu¹, Philaphon Sayavong^{1

4}, Stacey F Bent², Jian Qin², Zhenan Bao², Yi Cui^{1

5

6}

Affiliations

¹ Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States.
² Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.
³ Materials Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720, United States.
⁴ Department of Chemistry, Stanford University, Stanford, California 94305, United States.
⁵ Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
⁶ Department of Energy Science and Engineering, Stanford University, Stanford, California 94305, United States.

PMID: 36700841
DOI: 10.1021/acsnano.2c12470

Abstract

Inorganic-rich solid-electrolyte interphases (SEIs) on Li metal anodes improve the electrochemical performance of Li metal batteries (LMBs). Therefore, a fundamental understanding of the roles played by essential inorganic compounds in SEIs is critical to realizing and developing high-performance LMBs. Among the prevalent SEI inorganic compounds observed for Li metal anodes, Li₃N is often found in the SEIs of high-performance LMBs. Herein, we elucidate new features of Li₃N by utilizing a suspension electrolyte design that contributes to the improved electrochemical performance of the Li metal anode. Through empirical and computational studies, we show that Li₃N guides Li electrodeposition along its surface, creates a weakly solvating environment by decreasing Li⁺-solvent coordination, induces organic-poor SEI on the Li metal anode, and facilitates Li⁺ transport in the electrolyte. Importantly, recognizing specific roles of SEI inorganics for Li metal anodes can serve as one of the rational guidelines to design and optimize SEIs through electrolyte engineering for LMBs.

Keywords: electrolyte engineering; lithium metal anode; lithium nitride; lithium solvation environment; lithium−metal battery; solid-electrolyte interphase; suspension electrolyte.