In Situ Construction of a LiF-Enriched Interfacial Modification Layer for Stable All-Solid-State Batteries

Tianpeng Jiao; Meng Xia; Zirong Chen; Yue Zou; Gaopan Liu; Ang Fu; Libao Chen; Zhengliang Gong; Yong Yang; Jianming Zheng

doi:10.1021/acsami.2c06700

In Situ Construction of a LiF-Enriched Interfacial Modification Layer for Stable All-Solid-State Batteries

ACS Appl Mater Interfaces. 2022 Jul 6;14(26):29878-29885. doi: 10.1021/acsami.2c06700. Epub 2022 Jun 24.

Authors

Tianpeng Jiao¹, Meng Xia¹, Zirong Chen¹, Yue Zou¹, Gaopan Liu¹, Ang Fu¹, Libao Chen², Zhengliang Gong³, Yong Yang^{1

4}, Jianming Zheng¹

Affiliations

¹ State Key Laboratory for Physical Chemistry of Solid Surface, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
² State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, China.
³ College of Energy, Xiamen University, Xiamen 361005, China.
⁴ Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen 361005, China.

PMID: 35749281
DOI: 10.1021/acsami.2c06700

Abstract

All-solid-state batteries (ASSBs), particularly based on sulfide solid-state electrolytes (SSEs), are expected to meet the requirements of high-energy-density energy storage. However, the unstable interface between the ceramic pellets and lithium (Li) metal can induce unconstrained Li-dendrite growth with safety concerns. Herein, we design a carbon fluoride-silver (CF_x-Ag) composite to modify the SSEs. As lithium fluoride (LiF) nanocrystals can be in situ formed through electrochemical reactions, this LiF-enriched modification layer with high surface energy can more effectively suppress Li dendrite penetration and interfacial reactions between the SSEs and anode. Remarkably, the all-solid-state symmetric cells using a lithium-boron alloy (LiB) anode can stably work to above 2,500 h under 0.5 mA cm^-2 and 2 mAh cm^-2 at 60 °C without shorting. A modified LiB||LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) full cell also demonstrates an improved capacity retention and high Coulombic efficiency (99.9%) over 500 cycles. This work provides an advanced solid-state interface architecture to address Li-dendrite issues of ASSBs.

Keywords: LiF nanocrystals; LiSiPSCl electrolyte; all-solid-state batteries; carbon fluoride−silver; interfacial stability; lithium−boron alloy anode.