Molecular Design of Nitrile Electrolytes Enabling Lithiated Silicon–Sulfur Batteries with Quasi‐Solid‐State Sulfur Reaction

M Mengxue He Y Yunpeng Fu (Key Laboratory of Theoretical Organic Chemistry and Functional Molecule, Ministry of Education; School of Chemistry and Chemical Engineering Hunan University of Science and Technology Xiangtan 411201 China) L Lujun Zhu (Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering) Y Yue Ma C Chenxi Zheng (International Center for Quantum Materials, School of Physics) G Guo Ye (State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, 38 Xueyuan Road, Beijing 100191, China) Z Zhitong Xiao (Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering) Y Yongfeng Jia (Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering) X Xin Gao M Mingchuan Luo (Peking University , , ,) K Kenneth Ozoemena (Molecular Sciences Institute School of Chemistry University of the Witwatersrand Private Bag 3, P O Wits Johannesburg 2050 South Africa) M Mohammadhosein Safari (Institute for Materials Research (IMO-imomec), Hasselt University, Martelarenlaan 42, Hasselt 3500, Belgium) S Shaojun Qiu (Key Laboratory of Theoretical Organic Chemistry and Functional Molecule, Ministry of Education; School of Chemistry and Chemical Engineering Hunan University of Science and Technology Xiangtan 411201 China) J Jinglun Wang Q Quanquan Pang

Abstract

Abstract The development of lithium–sulfur (Li−S) batteries is hindered by the polysulfide dissolving, cross‐over and the inherent lithium metal anode instability. We herein instead describe a lithiated silicon−sulfur (LiSi−S) battery enabled by molecular engineering of highly solvating nitrile electrolytes toward weakly solvating to fundamentally decouple the reactions of the two electrodes and eliminate their cross‐talk. Specifically, by controlled fluorination of the ethoxy‐nitrile base solvent, the charge distribution on the solvent is manipulated which suppresses the solvation for polysulfides promoting a quasi‐solid‐state sulfur reaction (QSSSR) mechanism. The promoted anion participation in Li + solvation, along with the fluoroethylene carbonate additive, further stabilizes the interphases at both sulfur cathode and LiSi anode mitigating the mechanical degradations. The QSSSR‐based LiSi−S cell shows a high capacity of 1499.0 mA h g sulfur −1 at 0.1C, and achieves a high capacity retention of 90.2% over 100 cycles at 0.2C with an average Coulombic efficiency of 99.9%. This work highlights the essence of molecular engineering for manipulating the primary reactions and interphasial behaviors at both electrodes toward high performance sulfur batteries.

Article Details

Volume / Issue Vol. 65, Issue 3
Published January 16, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (15)

M

Mengxue He

Y

Yunpeng Fu

Key Laboratory of Theoretical Organic Chemistry and Functional Molecule, Ministry of Education; School of Chemistry and Chemical Engineering Hunan University of Science and Technology Xiangtan 411201 China

L

Lujun Zhu

Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering

Y

Yue Ma

C

Chenxi Zheng

International Center for Quantum Materials, School of Physics

G

Guo Ye

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, 38 Xueyuan Road, Beijing 100191, China

Z

Zhitong Xiao

Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering

Y

Yongfeng Jia

Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering

X

Xin Gao

M

Mingchuan Luo

Peking University , , ,

K

Kenneth Ozoemena

Molecular Sciences Institute School of Chemistry University of the Witwatersrand Private Bag 3, P O Wits Johannesburg 2050 South Africa

M

Mohammadhosein Safari

Institute for Materials Research (IMO-imomec), Hasselt University, Martelarenlaan 42, Hasselt 3500, Belgium

S

Shaojun Qiu

Key Laboratory of Theoretical Organic Chemistry and Functional Molecule, Ministry of Education; School of Chemistry and Chemical Engineering Hunan University of Science and Technology Xiangtan 411201 China

J

Jinglun Wang

Q

Quanquan Pang