<p>Quasi-solid-state electrolytes (QSEs) are critical for ultrafast-charging yet high-safety sodium metal batteries (SMBs), yet their implementation is hindered by sluggish Na<sup>+</sup> transport in bulk and at interfaces. Here, we propose dual interlocked mediator engineering that transcends conventional independent approaches by coupling cationic Sn<sup>2+</sup> salt with anionic difluoro(oxalato)borate (DFOB⁻) salts to simultaneously regulating bulk ion transport and bilateral interface chemistry. During QSE preparation, Sn<sup>2+</sup> initiates in situ cationic polymerization, while DFOB⁻ acts as a retarding agent to suppress runaway polymerization. The first interlocking effect in the Sn-FB QSE bulk builds a uniform network, enabling near-unity Na<sup>+</sup> transference number (0.94) and robust puncture strength (8.5&#xa0;kPa). During cell operation, Sn<sup>2+</sup> is reduced to form a hybrid NaSn alloy-based solid-electrolyte interphase, while DFOB⁻ oxidizes to generate a robust yet thin cathode–electrolyte interphase, respectively. This second interlocking effect creates adaptable bilateral interphases that facilitate Na<sup>+</sup> diffusion and mitigate interfacial degradation. As a result, the symmetric cells exhibit 6000&#xa0;h stability, and full cells retain 80.1&#xa0;mAh&#xa0;g<sup>–1</sup> at an ultrafast-charging rate of 15C and retain 90% capacity at 3C over 2000 cycles. Furthermore, high-mass-loading full cells and pressure-free pouch cells are demonstrated, underscoring the potential of dual interlocked mediator engineering for practical SMBs.</p>

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Dual Interlocked Mediators Enable Single-Ion-Conducting Quasi-Solid-State Electrolytes for Ultrafast-Charging Long-Life Sodium Metal Batteries

  • Yuan Zhang,
  • Long Pan,
  • Cheong Wa Leong,
  • Xing-Guo Qi,
  • Xiaozhong Huang,
  • Xinyi Cai,
  • Mufan Cao,
  • Min Gao,
  • Haoyu Zhang,
  • Dawei Sha,
  • Yang Zhou,
  • ZhengMing Sun

摘要

Quasi-solid-state electrolytes (QSEs) are critical for ultrafast-charging yet high-safety sodium metal batteries (SMBs), yet their implementation is hindered by sluggish Na+ transport in bulk and at interfaces. Here, we propose dual interlocked mediator engineering that transcends conventional independent approaches by coupling cationic Sn2+ salt with anionic difluoro(oxalato)borate (DFOB⁻) salts to simultaneously regulating bulk ion transport and bilateral interface chemistry. During QSE preparation, Sn2+ initiates in situ cationic polymerization, while DFOB⁻ acts as a retarding agent to suppress runaway polymerization. The first interlocking effect in the Sn-FB QSE bulk builds a uniform network, enabling near-unity Na+ transference number (0.94) and robust puncture strength (8.5 kPa). During cell operation, Sn2+ is reduced to form a hybrid NaSn alloy-based solid-electrolyte interphase, while DFOB⁻ oxidizes to generate a robust yet thin cathode–electrolyte interphase, respectively. This second interlocking effect creates adaptable bilateral interphases that facilitate Na+ diffusion and mitigate interfacial degradation. As a result, the symmetric cells exhibit 6000 h stability, and full cells retain 80.1 mAh g–1 at an ultrafast-charging rate of 15C and retain 90% capacity at 3C over 2000 cycles. Furthermore, high-mass-loading full cells and pressure-free pouch cells are demonstrated, underscoring the potential of dual interlocked mediator engineering for practical SMBs.