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<p>Abundant sodium (Na) batteries are a sustainable alternative to resource-constrained lithium-ion batteries, offering huge cost advantages. However, developing high-voltage anode-free sodium metal batteries (SMBs) to narrow the energy density gap with lithium-ion batteries is hindered by a critical challenge: existing electrolytes cannot simultaneously achieve ultra-high Na coulombic efficiency and anodic stability. Here we present a rationally designed non-fluorinated electrolyte (1.0 M NaPF<sub>6</sub> in 1,2-diethoxyethane/1,2-di-<i>tert</i>-butoxyethane) to address this key limitation, achieving Na coulombic efficiency of &gt;99.95% and anodic stability of &gt;4.8 V. For coin cells (2.0 mAh cm<sup>−2</sup>, N/P = 1.7), our electrolyte design enables 4.0 V Na | |Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP) at 5 C and 4.3 V Na | |NaNi<sub>0.6</sub>Mn<sub>0.2</sub>Co<sub>0.2</sub>O<sub>2</sub> (NMC622) at 0.3 C for 5,000 and 500 cycles with a capacity retention &gt;80%. Remarkably, the 50 mAh anode-free pouch cells 4.0 V Al | |NVP and 4.3 V Al | |NMC622 also achieve 500 and 300 cycles (retention &gt;75%) with a specific energy of &gt;360 Wh kg<sub>(electrode)</sub><sup>−1</sup>. This work focuses on electrolyte optimization and conceptual advances, whereas critical aspects such as safety, large-scale manufacturability and practical feasibility of SMBs require further investigation. The electrolyte design using non-fluorinated solvents enhances the anodic stability without sacrificing Na efficiency, laying groundwork for advancing low-cost, high-energy SMBs and supporting the transition to sustainable battery technologies.</p>

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Non-fluorinated electrolyte for high-voltage anode-free sodium metal battery

  • 期刊论文

  • 发表日期：

    2025年12月8日

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  • Ai-Min Li,
  • Travis P. Pollard,
  • Zeyi Wang,
  • Nan Zhang,
  • Fred Omenya,
  • Sha Tan,
  • Enyuan Hu,
  • Xiao-Qing Yang,
  • Xiaolin Li,
  • Oleg Borodin,
  • Chunsheng Wang

摘要

Abundant sodium (Na) batteries are a sustainable alternative to resource-constrained lithium-ion batteries, offering huge cost advantages. However, developing high-voltage anode-free sodium metal batteries (SMBs) to narrow the energy density gap with lithium-ion batteries is hindered by a critical challenge: existing electrolytes cannot simultaneously achieve ultra-high Na coulombic efficiency and anodic stability. Here we present a rationally designed non-fluorinated electrolyte (1.0 M NaPF6 in 1,2-diethoxyethane/1,2-di-tert-butoxyethane) to address this key limitation, achieving Na coulombic efficiency of >99.95% and anodic stability of >4.8 V. For coin cells (2.0 mAh cm−2, N/P = 1.7), our electrolyte design enables 4.0 V Na | |Na3V2(PO4)3 (NVP) at 5 C and 4.3 V Na | |NaNi0.6Mn0.2Co0.2O2 (NMC622) at 0.3 C for 5,000 and 500 cycles with a capacity retention >80%. Remarkably, the 50 mAh anode-free pouch cells 4.0 V Al | |NVP and 4.3 V Al | |NMC622 also achieve 500 and 300 cycles (retention >75%) with a specific energy of >360 Wh kg(electrode)−1. This work focuses on electrolyte optimization and conceptual advances, whereas critical aspects such as safety, large-scale manufacturability and practical feasibility of SMBs require further investigation. The electrolyte design using non-fluorinated solvents enhances the anodic stability without sacrificing Na efficiency, laying groundwork for advancing low-cost, high-energy SMBs and supporting the transition to sustainable battery technologies.