Anchoring and Competition: Weakly Solvated Structure of Glymes Enhances Stability in Lithium Metal Batteries Operating under Extreme Conditions

T Tianle Zheng M Mengqi Wu J Jianwei Xiong (Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies College of Materials Science and Technology Nanjing University of Aeronautics and Astronautics Nanjing 211106 P.R. China) M Ming Yang W Wenzhe Guo (Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany) Q Qihan Zeng (Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany) H Hongwei Yu (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals) T Tonghui Xu W Weiping Xie (Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China) Y Yiyao Xiao (Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China) Z Zhuijun Xu (Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany) Y Yuxin Liang Z Zerui Li R Ruoxuan Qi (Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany) G Guangjiu Pan (TUM School of Natural Sciences, Chair for Functional Materials, Physics Department, Technical University of Munich, James-Franck-Str. 1, 85748 Garching, Germany) X Xiaotang Shi (Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China) H Hongbin Zhao (Department of Chemistry and Institute for Sustainable Energy/College of Sciences) X Xiaohong Li (Key Laboratory of Theoretical & Computational Photochemistry of Ministry of Education, College of Chemistry) Y Yongyao Xia Y Ya‐Jun Cheng (Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China) Y Yonggao Xia (Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China) P Peter Müller‐Buschbaum (TUM School of Natural Sciences Department of Physics Chair for Functional Materials Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany)

Abstract

AbstractLithium metal batteries (LMBs) face challenges from unstable and fragile solid electrolyte interphases (SEIs). In this work, we successfully develop a novel electrolyte by effectively modulating the competitive solvation process in LMBs. In this formulation, the C─O─C motifs of glymes are competitively substituted by other anions and solvents to achieve single oxygen site coordination, thereby facilitating a weak solvation effect. At an apparent concentration of 1.25 M, a solvated sheath enriched with anions and single oxygen‐bound complexes is formed, which significantly enhances lithium metal compatibility and promotes rapid desolvation kinetics. The designed electrolyte using weakly solvated structures exhibits remarkable stability at both 25° and 80 °C, enabling the lithium iron phosphate (LFP)||Li cell to achieve over 2000 cycles (capacity retention: 90%) and 500 cycles (capacity retention: 96%), respectively. Interestingly, the low N/P ratio LFP||Li (N/P = 1.8) full battery maintains a stable capacity over 50 cycles, and the commercial 1.1 Ah LFP||Li pouch cell shows a great stability (capacity retention: 91.0%, CE: 99.82%) over 20 cycles. The distinctive solvation regulation strategy has paved a novel research avenue for the realization of high‐performance LMBs.

Article Details

Volume / Issue Vol. 64, Issue 40
Published September 26, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (22)

T

Tianle Zheng

M

Mengqi Wu

J

Jianwei Xiong

Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies College of Materials Science and Technology Nanjing University of Aeronautics and Astronautics Nanjing 211106 P.R. China

M

Ming Yang

W

Wenzhe Guo

Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany

Q

Qihan Zeng

Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany

H

Hongwei Yu

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals

T

Tonghui Xu

W

Weiping Xie

Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China

Y

Yiyao Xiao

Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China

Z

Zhuijun Xu

Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany

Y

Yuxin Liang

Z

Zerui Li

R

Ruoxuan Qi

Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany

G

Guangjiu Pan

TUM School of Natural Sciences, Chair for Functional Materials, Physics Department, Technical University of Munich, James-Franck-Str. 1, 85748 Garching, Germany

X

Xiaotang Shi

Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China

H

Hongbin Zhao

Department of Chemistry and Institute for Sustainable Energy/College of Sciences

X

Xiaohong Li

Key Laboratory of Theoretical & Computational Photochemistry of Ministry of Education, College of Chemistry

Y

Yongyao Xia

Y

Ya‐Jun Cheng

Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China

Y

Yonggao Xia

Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences 1219 Zhongguan West Rd Ningbo Zhejiang Province 315201 P.R. China

P

Peter Müller‐Buschbaum

TUM School of Natural Sciences Department of Physics Chair for Functional Materials Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany