Electrostatic Regulation of Na+ Coordination Chemistry for High‑Performance All‑Solid‑State Sodium Batteries

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Electrostatic Regulation of Na+ Coordination Chemistry for High‑Performance All‑Solid‑State Sodium Batteries
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Electrostatic Regulation of Na+ Coordination Chemistry for High-Performance All-Solid-State Sodium Batteries - Nano-Micro Letters

Ion migration capability and interfacial chemistry of solid polymer electrolytes (SPEs) in all-solid-state sodium metal batteries (ASSMBs) are closely related to the Na+ coordination environment. Herein, an electrostatic engineering strategy is proposed to regulate the Na+ coordinated structure by employing a fluorinated metal–organic framework as an electron-rich model. Theoretical and experimental results revealed that the abundant electron-rich F sites can accelerate the disassociation of Na-salt through electrostatic attraction to release free Na+, while forcing anions into a Na+ coordination structure though electrostatic repulsion to weaken the Na+ coordination with polymer, thus promoting rapid Na+ transport. The optimized anion-rich weak solvation structure fosters a stable inorganic-dominated solid–electrolyte interphase, significantly enhancing the interfacial stability toward Na anode. Consequently, the Na/Na symmetric cell delivered stable Na plating/stripping over 2500 h at 0.1 mA cm−2. Impressively, the assembled ASSMBs demonstrated stable performance of over 2000 cycles even under high rate of 2 C with capacity retention nearly 100%, surpassing most reported ASSMBs using various solid-state electrolytes. This work provides a new avenue for regulating the Na+ coordination structure of SPEs by exploration of electrostatic effect engineering to achieve high-performance all-solid-state alkali metal batteries. Graphical Abstract

As demand for safer, higher-energy batteries surges, all-solid-state sodium-metal batteries (ASSMBs) promise a low-cost, non-flammable alternative to Li-ion technology. Yet their practical use is stymied by sluggish Na+ transport and poor interfacial stability. Now, a joint team from Jiangnan University, Henan Academy of Sciences and University of Bayreuth, led by Prof. Suli Chen, Dr. Qiongqiong Lu and Prof. Qingsong Wang, presents an electrostatic-engineering strategy that redesigns the Na⁺ coordination shell inside polymer electrolytes and delivers >2000 stable cycles at 2 C—a new benchmark for ASSMBs.

Why Electrostatic Control Matters

  • Faster Na+ Conduction: Weakening Na+–ether oxygen bonds cuts desolvation barriers, boosting ionic conductivity to 1.01 mS cm-1 at 60 °C.
  • Stable Na-Metal Interface: An anion-rich solvation sheath forms an inorganic-rich, NaF/Na3N SEI that suppresses dendrites for 2500 h of symmetric-cell cycling.
  • High-Power Performance: Full cells retain ≈100 % capacity over 2000 cycles at 2 C, outperforming most reported solid-state sodium systems.

Innovative Design and Features

  • Fluorinated MOF (UiO-66-(F)4) as Electron-Rich Beacon: High-density F sites electrostatically attract Na+ and repel TFSI-, driving salt dissociation while forcing anions into the primary solvation structure.
  • Weakened Na+–PEO Coordination: RDF, ss-NMR and Raman analyses confirm shortened Na–O(ether) bonds and increased Na–O(TFSI-) contacts, creating a “weak” solvation environment that accelerates bulk and interfacial transport.
  • Mechanically Robust Membrane: 9 wt % FMOF yields 4.4 MPa tensile strength and 1350 % elongation, suppressing dendrites while maintaining processability.
  • Scalable Fabrication: Solution-casting produces < 80 µm, flexible, transparent films in an Ar glove box—compatible with roll-to-roll assembly.

Applications and Future Outlook

  • Practical Pouch Cells: An 11.6 mg cm-2 NVP cathode paired with PEO-FMOF delivers 86 % capacity retention after 250 cycles at 0.5 C and survives folding/cutting abuse tests, highlighting safety for wearable or flexible devices.
  • Universal Electrostatic Concept: The FMOF platform can be extended to Li+, K+ and Zn2+systems, offering a general toolkit to tune cation solvation in any solid polymer electrolyte.
  • Next Steps: The team is scaling film width to > 10 cm, optimizing MOF cost and exploring dry-electrode hot-pressing for greener manufacturing.

This work demonstrates that electrostatic engineering at the molecular level can simultaneously solve the ion-transport and interfacial challenges that have long hindered solid-state sodium batteries. Stay tuned for more high-power, long-life energy-storage innovations from the collaborative labs of Jiangnan University and BayBatt!

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Batteries
Physical Sciences > Materials Science > Materials for Energy and Catalysis > Batteries
Electrochemistry
Physical Sciences > Chemistry > Physical Chemistry > Electrochemistry
Surfaces, Interfaces and Thin Film
Physical Sciences > Materials Science > Surfaces, Interfaces and Thin Film
Reaction Kinetics
Physical Sciences > Chemistry > Physical Chemistry > Reaction Kinetics
Metal-organic Frameworks
Physical Sciences > Materials Science > Materials for Energy and Catalysis > Metal-organic Frameworks
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