Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries

Abstract The ether-based electrolytes are acknowledged for their compatibility with a diverse array of sodium-ion battery anodes, as well as their capability to enable efficient and reversible electrochemical reactions. However, they encounter a challenge of oxidation at high voltages. We find that...

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Main Authors: Xingyu Wang, Qi Fan, Ziheng Liu, Xinyue Zhu, Mei Yang, Zhiyuan Guo, Yuting Chen, Liuqi Wang, Yu Jing, Hui Xia
Format: Article
Language:English
Published: Nature Portfolio 2025-03-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-57910-7
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author Xingyu Wang
Qi Fan
Ziheng Liu
Xinyue Zhu
Mei Yang
Zhiyuan Guo
Yuting Chen
Liuqi Wang
Yu Jing
Hui Xia
author_facet Xingyu Wang
Qi Fan
Ziheng Liu
Xinyue Zhu
Mei Yang
Zhiyuan Guo
Yuting Chen
Liuqi Wang
Yu Jing
Hui Xia
author_sort Xingyu Wang
collection DOAJ
description Abstract The ether-based electrolytes are acknowledged for their compatibility with a diverse array of sodium-ion battery anodes, as well as their capability to enable efficient and reversible electrochemical reactions. However, they encounter a challenge of oxidation at high voltages. We find that a standard diglyme-based electrolyte starts to oxidize and break down at voltages exceeding 3.9 V (vs. Na+/Na). This deterioration is attributed to the nucleophilic nature of the diglyme solvent and the presence of oxygen atoms that possess two unpaired electrons. To address this issue, we incorporate foreign anions into the electrolyte system to passivate the reactive sites of terminal H on diglyme solvents, inhibiting further dehydrogenation and oxidation during battery operation. The constructed cathode electrolyte interphase, enriched with NaF and NaNxOy, substantially boosts the oxidation resistance of electrolyte to over 4.8 V (vs. Na+/Na), expanding the stability window and rendering it feasible for various high-voltage cathode materials. Our approach also ensures compatibility with either hard carbon or commercial graphite anodes, guaranteeing operation in pouch cells. This study elucidates the relationship between interfacial chemistry and oxidation tolerance at high voltages, offering an approach to the development of practical ether-based electrolytes for high-energy-density battery technologies.
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issn 2041-1723
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spelling doaj-art-fd6464b347734261aee8aa1ac1331a9e2025-08-20T03:01:39ZengNature PortfolioNature Communications2041-17232025-03-011611910.1038/s41467-025-57910-7Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteriesXingyu Wang0Qi Fan1Ziheng Liu2Xinyue Zhu3Mei Yang4Zhiyuan Guo5Yuting Chen6Liuqi Wang7Yu Jing8Hui Xia9School of Materials Science and Engineering, Nanjing University of Science and TechnologySchool of Materials Science and Engineering, Nanjing University of Science and TechnologySchool of Materials Science and Engineering, Nanjing University of Science and TechnologyJiangsu Co-Innovation Centre of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry UniversitySchool of Materials Science and Engineering, Nanjing University of Science and TechnologySchool of Materials Science and Engineering, Nanjing University of Science and TechnologySchool of Materials Science and Engineering, Nanjing University of Science and TechnologySchool of Materials Science and Engineering, Nanjing University of Science and TechnologyJiangsu Co-Innovation Centre of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry UniversitySchool of Materials Science and Engineering, Nanjing University of Science and TechnologyAbstract The ether-based electrolytes are acknowledged for their compatibility with a diverse array of sodium-ion battery anodes, as well as their capability to enable efficient and reversible electrochemical reactions. However, they encounter a challenge of oxidation at high voltages. We find that a standard diglyme-based electrolyte starts to oxidize and break down at voltages exceeding 3.9 V (vs. Na+/Na). This deterioration is attributed to the nucleophilic nature of the diglyme solvent and the presence of oxygen atoms that possess two unpaired electrons. To address this issue, we incorporate foreign anions into the electrolyte system to passivate the reactive sites of terminal H on diglyme solvents, inhibiting further dehydrogenation and oxidation during battery operation. The constructed cathode electrolyte interphase, enriched with NaF and NaNxOy, substantially boosts the oxidation resistance of electrolyte to over 4.8 V (vs. Na+/Na), expanding the stability window and rendering it feasible for various high-voltage cathode materials. Our approach also ensures compatibility with either hard carbon or commercial graphite anodes, guaranteeing operation in pouch cells. This study elucidates the relationship between interfacial chemistry and oxidation tolerance at high voltages, offering an approach to the development of practical ether-based electrolytes for high-energy-density battery technologies.https://doi.org/10.1038/s41467-025-57910-7
spellingShingle Xingyu Wang
Qi Fan
Ziheng Liu
Xinyue Zhu
Mei Yang
Zhiyuan Guo
Yuting Chen
Liuqi Wang
Yu Jing
Hui Xia
Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries
Nature Communications
title Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries
title_full Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries
title_fullStr Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries
title_full_unstemmed Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries
title_short Anion-mediated approach to overcome oxidation in ether electrolytes for high-voltage sodium-ion batteries
title_sort anion mediated approach to overcome oxidation in ether electrolytes for high voltage sodium ion batteries
url https://doi.org/10.1038/s41467-025-57910-7
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