Ether-Oxygen Groups Modified Carboxylic Ester Enabling High-Voltage Lithium Metal Batteries

Shuang Li; Hongliang Xie; Pushpendra Kumar; Yinghua Chen; Jia Wang; Akang Huang; Wandi Wahyudi; Hui Zhu; Jiao Yin; Qian Li; Zheng Ma; Jun Ming

doi:10.1002/anie.202504490

Ether-Oxygen Groups Modified Carboxylic Ester Enabling High-Voltage Lithium Metal Batteries

Angew Chem Int Ed Engl. 2025 May 23:e202504490. doi: 10.1002/anie.202504490. Online ahead of print.

Authors

Shuang Li^{1

2}, Hongliang Xie¹, Pushpendra Kumar³, Yinghua Chen^{1

2}, Jia Wang^{1

2}, Akang Huang^{1

2}, Wandi Wahyudi⁴, Hui Zhu⁵, Jiao Yin⁵, Qian Li¹, Zheng Ma¹, Jun Ming^{1

2}

Affiliations

¹ State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.
² School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, China.
³ School of Physical Sciences, Jawaharlal Nehru University, New Delhi, 110067, India.
⁴ Materials Science and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
⁵ Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi, 830011, China.

PMID: 40407398
DOI: 10.1002/anie.202504490

Abstract

Lithium metal batteries (LMBs) operating at high cut-off voltages can achieve an energy density exceeding 500 Wh kg^-1; however, they often suffer from severe capacity degradation due to electrolyte decomposition. Herein, propylene glycol monomethyl ether acetate (PMA) is introduced as a novel solvent for LMB electrolytes. The unique ether-oxygen functionality in PMA exhibits high steric hindrance, leading to weak lithium-ion coordination, which promotes the formation of contact ion pairs (CIPs) in the electrolyte solvation structure, especially in the presence of dual salts. A Li||LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) battery employing the formulated PMA-based electrolyte demonstrates stable cycling at a high cut-off voltage of 4.5 V for over 100 cycles, retaining 90.1% of its initial capacity even at 60 °C. Furthermore, a molecular interfacial model is proposed to elucidate the impact of the designed electrolyte on electrode interfacial behavior and battery performance, providing valuable insights for the development of high-performance LMB electrolytes.

Keywords: Contact ion pairs; De‐solvation behaviors; Electrolyte solvation structure; Lithium metal batteries; Molecular design.

Abstract

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