Understanding the failure process of sulfide-based all-solid-state lithium batteries via operando nuclear magnetic resonance spectroscopy

Ziteng Liang; Yuxuan Xiang; Kangjun Wang; Jianping Zhu; Yanting Jin; Hongchun Wang; Bizhu Zheng; Zirong Chen; Mingming Tao; Xiangsi Liu; Yuqi Wu; Riqiang Fu; Chunsheng Wang; Martin Winter; Yong Yang

doi:10.1038/s41467-023-35920-7

Understanding the failure process of sulfide-based all-solid-state lithium batteries via operando nuclear magnetic resonance spectroscopy

Nat Commun. 2023 Jan 17;14(1):259. doi: 10.1038/s41467-023-35920-7.

Authors

Ziteng Liang^#¹, Yuxuan Xiang^#^{1

2}, Kangjun Wang¹, Jianping Zhu¹, Yanting Jin¹, Hongchun Wang³, Bizhu Zheng¹, Zirong Chen¹, Mingming Tao¹, Xiangsi Liu¹, Yuqi Wu³, Riqiang Fu⁴, Chunsheng Wang⁵, Martin Winter^{6

7}, Yong Yang^{8

9}

Affiliations

¹ State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
² School of Engineering, Westlake University, Hangzhou, Zhejiang, 310030, China.
³ College of Energy, Xiamen University, Xiamen, 361005, China.
⁴ National High Magnetic Field Laboratory, Tallahassee, FL, USA.
⁵ Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, 20740, USA.
⁶ MEET Battery Research Center, Institute of Physical Chemistry, University of Münster, 48149, Münster, Germany.
⁷ Helmholtz Institute Münster (IEK-12), Forschungszentrum Jülich GmbH, 48149, Münster, Germany.
⁸ State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. yyang@xmu.edu.cn.
⁹ College of Energy, Xiamen University, Xiamen, 361005, China. yyang@xmu.edu.cn.

^# Contributed equally.

Abstract

The performance of all-solid-state lithium metal batteries (SSLMBs) is affected by the presence of electrochemically inactive (i.e., electronically and/or ionically disconnected) lithium metal and solid electrolyte interphase (SEI), which are jointly termed inactive lithium. However, the differentiation and quantification of inactive lithium during cycling are challenging, and their lack limits the fundamental understanding of SSLMBs failure mechanisms. To shed some light on these crucial aspects, here, we propose operando nuclear magnetic resonance (NMR) spectroscopy measurements for real-time quantification and evolution-tracking of inactive lithium formed in SSLMBs. In particular, we examine four different sulfide-based solid electrolytes, namely, Li₁₀GeP₂S₁₂, Li_9.54Si_1.74P_1.44S_11.7Cl_0.3, Li₆PS₅Cl and Li₇P₃S₁₁. We found that the chemistry of the solid electrolyte influences the activity of lithium. Furthermore, we demonstrate that electronically disconnected lithium metal is mainly found in the interior of solid electrolytes, and ionically disconnected lithium metal is found at the negative electrode surface. Moreover, by monitoring the Li NMR signal during cell calendar ageing, we prove the faster corrosion rate of mossy/dendritic lithium than flat/homogeneous lithium in SSLMBs.

Grants and funding

22261160570, 21935009 and 22021001/National Natural Science Foundation of China (National Science Foundation of China)