article · Advanced Functional Materials
High-voltage sodium-ion batteries often experience rapid capacity loss because fragile cathode interphases and continuous solid-electrolyte interphase growth on anodes cause electron leakage. To resolve this challenge, an electrolyte formulation based on cooperative sodium-ion solvation combines soft and moderate co-solvents to regulate interphase chemistry. This controlled solvation behaviour produces stable protective interphases with optimal thickness across both electrodes. In laboratory testing, high-voltage Na3V2O2(PO4)2F cathodes retained 83.3 percent of their capacity after 3000 cycles at a 1 C rate, markedly exceeding the 41.6 percent retention observed with standard carbonate electrolytes. Furthermore, curtailing the generation of electron-leaking sodium carbonate improved the long-term stability of hard carbon anodes. Full cells combining these components demonstrated high-rate capability up to 15 C and maintained stable operation across 500 cycles.
Sodium-ion batteries offer an abundant and lower-cost alternative to lithium-ion systems, yet their adoption has been limited by rapid degradation at high operating voltages. By overcoming interphase instability through smart electrolyte design, this development substantially increases battery longevity and charge rates. Such improvements are vital for making sodium-ion chemistries viable for high-performance and grid-scale energy storage.
This research is applicable to battery component manufacturers and energy storage companies developing durable, non-lithium chemistries. The technology is at an applied research stage, having been validated in experimental full cells under high-rate and multi-hundred-cycle conditions. Transitioning towards commercial use will require pilot-scale electrolyte synthesis, industrial cell format testing, and economic evaluation alongside existing manufacturing lines.
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Abstract Stabilizing the electrode interphases is urgently required to enhance the lifetime of high‐voltage sodium‐ion batteries (SIBs). However, the continuous anode solid–electrolyte interphase (SEI) growth associated with electron leakage and the fragile cathode–electrolyte interphase (CEI) lead to capacity fade at high voltage; and yet the solvation‐interphase‐performance relationship is inadequately addressed. Herein, a cooperative Na + ‐solvation strategy is reported to stabilize the interphases by a holistic design of electrolytes combining soft and moderate co‐solvents. The rationally regulated Na + ‐solvation leads to CEI/SEI with the desired thickness and component stability. As such, remarkable cycling stability is achieved for 4.3‐V Na 3 V 2 O 2 (PO 4 ) 2 F (NVOPF) cathodes with 83.3% capacity retention over 3000 cycles at 1 C, significantly outperforming the carbonate counterpart (41.6% capacity retention). Meanwhile, the restrained SEI growth via reducing the formation of electron‐leaking Na 2 CO 3 stabilizes the long‐term cycling of the hard carbon (HC) anode. The assembled NVOPF||HC full cells achieve superior rate capability (up to 15 C) and stable cycling stability over 500 cycles. The demonstrated engineering of electrolyte chemistry, Na + ‐solvation, and interphase structure/component contributes toward the rational establishment of design rules for high‐voltage SIBs and possibly other similar chemistries.
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DOI: 10.1002/adfm.202403138
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