Evaluating the performance and practical viability of Glyme-Based Electrolytes for anode-free Na-cells
Abstract
Anode-free sodium metal batteries (AFSMBs), as a potential strategy for achieving high energy density, have garnered considerable interest recently due to their demonstrated stable cycling performance when paired with ether- or glyme-based electrolytes. Therefore, to assess the practical viability of anode-free sodium cells, we investigate here the electrochemical behavior of a sodium layered oxide Na0.85Ni0.38Zn0.04Mn0.48Ti0.1O2 (ZNMT) and a polyanionic Na4Fe3(PO4)2P2O7 (NFPP) positive electrodes versus carbon-coated aluminum (ccAl) current collector using 1 M NaPF6 in diglyme as the electrolyte. Although sodium reservoir helps improving the cycling stability of ZNMT|ccAl cells, the oxidation of diglyme, even at 3.8 V, partially contributes to capacity degradation, thereby limiting the use of diglyme to low-voltage NFPP|ccAl cells (<3.5 V vs Na+/Na0). Furthermore, by combining complementary studies on NFPP|ccAl and Na|ccAl cells, we show that parasitic chemical and electrochemical reactions between metallic sodium and the electrolyte contribute to capacity fade and self-discharge during rest, with these effects becoming more pronounced at elevated temperatures. This reactivity is reduced, but still persists while replacing ccAl with Zn current collector, where NFPP|Zn cell deliver improved performance of 80% capacity retention for ~100 cycles (~1000 h) vs ~50 cycles (~500 h) for NFPP|ccAl cell. Our findings highlight both the opportunities and the intrinsic limitations of glyme-based electrolytes for anode-free sodium cells. Furthermore, we propose critical electrochemical evaluation criteria that extend beyond cycle-life metrics, enabling more meaningful comparison of anode-free cells across different electrode configurations, loadings, and operating conditions.
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BibTeX
@article{barillon2026evaluating,
title = {{Evaluating the performance and practical viability of Glyme-Based Electrolytes for anode-free Na-cells}},
author = {Adèle Barillon and Jazer Jose H. Togonon and Hugo Chotard and Parth Desai and Paul Naillou and Guochun Yan and Sandrine Lyonnard and Sathiya Mariyappan},
journal = {EES Batteries},
year = {2026},
month = sep,
doi = {10.1039/d6eb00155f},
url = {https://hal.science/hal-05794661v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - Evaluating the performance and practical viability of Glyme-Based Electrolytes for anode-free Na-cells
AU - Adèle Barillon
AU - Jazer Jose H. Togonon
AU - Hugo Chotard
AU - Parth Desai
AU - Paul Naillou
AU - Guochun Yan
AU - Sandrine Lyonnard
AU - Sathiya Mariyappan
PY - 2026
DA - 2026/09/09
JO - EES Batteries
DO - 10.1039/d6eb00155f
UR - https://hal.science/hal-05794661v1
AB - Anode-free sodium metal batteries (AFSMBs), as a potential strategy for achieving high energy density, have garnered considerable interest recently due to their demonstrated stable cycling performance when paired with ether- or glyme-based electrolytes. Therefore, to assess the practical viability of anode-free sodium cells, we investigate here the electrochemical behavior of a sodium layered oxide Na0.85Ni0.38Zn0.04Mn0.48Ti0.1O2 (ZNMT) and a polyanionic Na4Fe3(PO4)2P2O7 (NFPP) positive electrodes versus carbon-coated aluminum (ccAl) current collector using 1 M NaPF6 in diglyme as the electrolyte. Although sodium reservoir helps improving the cycling stability of ZNMT|ccAl cells, the oxidation of diglyme, even at 3.8 V, partially contributes to capacity degradation, thereby limiting the use of diglyme to low-voltage NFPP|ccAl cells (<3.5 V vs Na+/Na0). Furthermore, by combining complementary studies on NFPP|ccAl and Na|ccAl cells, we show that parasitic chemical and electrochemical reactions between metallic sodium and the electrolyte contribute to capacity fade and self-discharge during rest, with these effects becoming more pronounced at elevated temperatures. This reactivity is reduced, but still persists while replacing ccAl with Zn current collector, where NFPP|Zn cell deliver improved performance of 80% capacity retention for ~100 cycles (~1000 h) vs ~50 cycles (~500 h) for NFPP|ccAl cell. Our findings highlight both the opportunities and the intrinsic limitations of glyme-based electrolytes for anode-free sodium cells. Furthermore, we propose critical electrochemical evaluation criteria that extend beyond cycle-life metrics, enabling more meaningful comparison of anode-free cells across different electrode configurations, loadings, and operating conditions.
SN - 3033-4071
ER -