Tetrahydrofuran (THF) Breakthrough in New Energy Battery Electrolytes: Balancing Low-Temperature Performance and Safety ——Optimizing Ionic Conductivity Across Wide Temperature Ranges

创建于03.19

1. ​The Low-Temperature Challenge in Lithium-Ion Batteries

Lithium-ion batteries face severe performance degradation in extreme temperatures. Below -20°C, traditional carbonate-based electrolytes suffer from sluggish ion transport, high desolvation energy barriers (~0.8 eV), and unstable solid-electrolyte interphases (SEI)
1. These limitations restrict applications in polar expeditions, electric vehicles in cold climates, and aerospace technologies.
Tetrahydrofuran (THF), a cyclic ether solvent, has emerged as a game-changer due to its ​low viscosity (0.55 cP at 25°C) and ​weak Li⁺-solvent interactions, enabling ultrafast ion migration even at subzero temperatures
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2. ​THF-Driven Electrolyte Design Innovations

2.1 Solvent Engineering: Disrupting Aggregated Ion Clusters

The ​THF-MTBE (methyl tert-butyl ether) hybrid solvent system (e.g., 0.25THMT electrolyte) effectively disrupts large ion aggregates (AGGs) that dominate conventional electrolytes
2. By forming ​contact ion pairs (CIPs), this system:
  • Reduces ionic migration resistance, increasing ionic conductivity ​from 0.27 to 4.21 mS/cm 
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  • Lowers the Li⁺ desolvation energy barrier, as evidenced by ​Arrhenius activation energy (Ea,ct) reduction 
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2.2 Wide-Temperature Performance Validation

  • At -40°C69% of room-temperature capacity
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  • Fast-Charging Capability
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3. ​Mechanistic Insights: Why THF Excels in Cryogenic Conditions

3.1 Solvation Structure Modulation

THF’s ​low donor number (DN=20.0) weakens Li⁺-solvent binding, promoting anion (e.g., TFSI⁻) participation in solvation shells. This facilitates:
  • Inorganic-Rich SEI Formation65% LiF/Li₂O 
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  • Suppressed Solvent Co-Intercalation

3.2 Thermal Resilience and Safety

  • Flame Retardancy
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  • SEI Stability Under Thermal Stress
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4. ​Synergistic Safety Strategies

4.1 Additive Optimization

  • Fluoroethylene Carbonate (FEC)
  • Lithium Nitrate (LiNO₃)
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4.2 Industrial Scalability Considerations

  • Cost-Effectiveness
  • Compatibility with High-Ni Cathodes
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5. ​Future Directions

5.1 Beyond Lithium-Ion: Multibattery Compatibility

THF’s design principles show promise for:
  • Sodium-Ion Batteries
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  • All-Solid-State Batteries

5.2 Sustainability Integration

  • Closed-Loop Recycling
  • Bio-THF Production

Conclusion

THF-based electrolytes represent a paradigm shift in balancing ​ultralow-temperature operation and ​intrinsic safety for next-gen batteries. By leveraging its unique solvation chemistry and coupling with advanced additives, THF unlocks:
  • Wide-Temperature Adaptability
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  • Scalable Manufacturing
As research progresses toward ​multivalent-ion systems and ​bio-sourced THF, this solvent will play a pivotal role in realizing energy-dense, fast-charging batteries for a carbon-neutral future.
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