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A Comparative Study of Solid Electrolyte Interphase Evolution in Ether and Ester-Based Electrolytes for Na-ion Batteries

Liang Zhao1,2,*, Sara I.R. Costa2,3,*, Yue Chen2,4,5, Jack R. Fitzpatrick1,2, Andrew J. Naylor6, Oleg Kolosov2,4, and Nuria Tapia-Ruiz1,2,3,†

  • *Contributed equally to this work.
  • †Contact author: n.tapia-ruiz@imperial.ac.uk
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PRX Energy 4, 033002 – Published 15 July, 2025

DOI: https://doi.org/10.1103/jfvb-wp5w

Abstract

The solid electrolyte interphase (SEI) largely determines the electrochemical performance of negative electrodes in sodium-ion batteries (SIBs). Ether-based electrolytes, such as diglyme, have been shown to form a more stable and thinner SEI on sodium anodes than traditional commercial ester-based electrolytes. Nonetheless, variations in the detailed evolution of the chemical composition and mechanical strength of the SEIs formed in these two electrolytic solutions during the electrochemical process have rarely been investigated. In this work, we conduct a comparative study of the SEI formed in diglyme-based and carbonate-based electrolytes with Na2Ti3O7 (NTO) as a proof-of-concept material, using energy-tuned photoelectron spectroscopy, operando electrochemical atomic force microscopy, and electrochemical techniques. The results show that diglyme forms a thin, homogeneous, and stable SEI with a well-defined inorganic-organic bilayer structure, as opposed to ester-based electrolytes, which form a thicker, nonuniform, and dynamically changing SEI with randomly distributed inorganic-organic structure. Moreover, the less resistive and higher capacitive interfacial processes induced by the diglyme-based electrolyte decrease the overall battery impedance. These advantages enable the NTO anode to exhibit superior specific capacity, cycle stability, and rate capability. This study provides an in-depth view of the factors behind the electrolyte-dependent performance of SIB anodes, which could inform the design and pairing of electrolytes with electrode materials in rechargeable batteries.

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Sodium-ion batteries are gaining attention as a cost-effective and sustainable alternative to lithium-ion batteries, but their long-term performance is limited by the instability of the solid electrolyte interphase (SEI)a protective layer that forms on the anode. In this study, the authors systematically compare SEI formation in ether-based (diglyme) and carbonate-based electrolytes, revealing how electrolyte chemistry influences SEI structure and stability. Using advanced spectroscopic and electrochemical techniques, they show that diglyme-based electrolytes promote a thin, uniform, and stable SEI with a well-organized inorganic/organic layered structure, which leads to lower interfacial impedance, improved Na transport, and enhanced cycling performance, significantly extending the battery's lifespan. These findings offer crucial insights into SEI evolution, guiding the development of optimized electrolyte formulations for next-generation sodium-ion batteries.

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PRX Energy 4, 033002– Published 15 July, 2025
  • Received 27 February 2025
  • Revised 28 April 2025
  • Accepted 12 May 2025
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