Polyfluorinated crosslinker-based solid polymer electrolytes for long-cycling 4.5 V lithium metal batteries

Lingfei Tang; Bowen Chen; Zhonghan Zhang; Changqi Ma; Junchao Chen; Yage Huang; Fengrui Zhang; Qingyu Dong; Guoyong Xue; Daiqian Chen; Chenji Hu; Shuzhou Li; Zheng Liu; Yanbin Shen; Qi Chen; Liwei Chen

doi:10.1038/s41467-023-37997-6

Polyfluorinated crosslinker-based solid polymer electrolytes for long-cycling 4.5 V lithium metal batteries

Nat Commun. 2023 Apr 21;14(1):2301. doi: 10.1038/s41467-023-37997-6.

Authors

Lingfei Tang^#^{1

2}, Bowen Chen^#^{1

2}, Zhonghan Zhang^#^{3

4}, Changqi Ma^#^{1

2}, Junchao Chen⁵, Yage Huang⁵, Fengrui Zhang², Qingyu Dong², Guoyong Xue⁵, Daiqian Chen², Chenji Hu⁵, Shuzhou Li⁴, Zheng Liu^{3

4}, Yanbin Shen^{1

2}, Qi Chen^{6

7}, Liwei Chen^{8

9

10}

Affiliations

¹ School of Nano-Tech and Nano-Bionics, University of Science and Technology of China, Hefei, 230026, China.
² i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China.
³ CINTRA CNRS/NTU/THALES, UMI 3288, Research Techno Plaza, Singapore, 637553, Singapore.
⁴ School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Ave, Singapore, 639798, Singapore.
⁵ School of Chemistry and Chemical Engineering, In situ Center for Physical Sciences, Shanghai Electrochemical Energy Device Research Center, and Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁶ School of Nano-Tech and Nano-Bionics, University of Science and Technology of China, Hefei, 230026, China. qchen2011@sinano.ac.cn.
⁷ i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China. qchen2011@sinano.ac.cn.
⁸ i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China. lwchen2018@sjtu.edu.cn.
⁹ School of Chemistry and Chemical Engineering, In situ Center for Physical Sciences, Shanghai Electrochemical Energy Device Research Center, and Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, 200240, China. lwchen2018@sjtu.edu.cn.
¹⁰ Solid-State Battery Research Center, Global Institute of Future Technology, Shanghai Jiao Tong University, Shanghai, 200240, China. lwchen2018@sjtu.edu.cn.

^# Contributed equally.

Abstract

Solid polymer electrolytes (SPEs), which are favorable to form intimate interfacial contacts with electrodes, are promising electrolyte of choice for long-cycling lithium metal batteries (LMBs). However, typical SPEs with easily oxidized oxygen-bearing polar groups exhibit narrow electrochemical stability window (ESW), making it impractical to increase specific capacity and energy density of SPE based LMBs with charging cut-off voltage of 4.5 V or higher. Here, we apply a polyfluorinated crosslinker to enhance oxidation resistance of SPEs. The crosslinked network facilitates transmission of the inductive electron-withdrawing effect of polyfluorinated segments. As a result, polyfluorinated crosslinked SPE exhibits a wide ESW, and the Li|SPE|LiNi_0.5Co_0.2Mn_0.3O₂ cell with a cutoff voltage of 4.5 V delivers a high discharge specific capacity of ~164.19 mAh g^-1 at 0.5 C and capacity retention of ~90% after 200 cycles. This work opens a direction in developing SPEs for long-cycling high-voltage LMBs by using polyfluorinated crosslinking strategy.