Rechargeable Li/Cl2 Battery Down to −80 °C

• Published in: Advanced materials (Weinheim) Vol. 36; no. 7; pp. e2307192 - n/a
• Main Authors: Liang, Peng, Zhu, Guanzhou, Huang, Cheng‐Liang, Li, Yuan‐Yao, Sun, Hao, Yuan, Bin, Wu, Shu‐Chi, Li, Jiachen, Wang, Feifei, Hwang, Bing‐Joe, Dai, Hongjie
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.02.2024
• Subjects: Activated carbon; Aluminum chloride; Batteries; Carbon; Carbon dioxide; Charging; Chlorine; Cl2 trapping; Cold weather; Discharge; Electrodes; Expeditions; high‐capacity; Ion currents; Lithium; Lithium chloride; Low temperature; Mass spectrometry; Oxidation; Photoelectrons; Rechargeable batteries; rechargeable lithium/chlorine battery; Sulfur chlorides; thionyl chloride (SOCl2); ultralow temperature
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202307192

Low temperature rechargeable batteries are important to life in cold climates, polar/deep‐sea expeditions, and space explorations. Here, this work reports 3.5–4 V rechargeable lithium/chlorine (Li/Cl2) batteries operating down to −80 °C, employing Li metal negative electrode, a novel carbon dioxide (CO2) activated porous carbon (KJCO2) as the positive electrode, and a high ionic conductivity (≈5–20 mS cm−1 from −80 °C to room‐temperature) electrolyte comprised of aluminum chloride (AlCl3), lithium chloride (LiCl), and lithium bis(fluorosulfonyl)imide (LiFSI) in low‐melting‐point (−104.5 °C) thionyl chloride (SOCl2). Between room‐temperature and −80 °C, the Li/Cl2 battery delivers up to ≈29 100–4500 mAh g−1 first discharge capacity (based on carbon mass) and a 1200–5000 mAh g−1 reversible capacity over up to 130 charge–discharge cycles. Mass spectrometry and X‐ray photoelectron spectroscopy probe Cl2 trapped in the porous carbon upon LiCl electro‐oxidation during charging. At −80 °C, Cl2/SCl2/S2Cl2 generated by electro‐oxidation in the charging step are trapped in porous KJCO2 carbon, allowing for reversible reduction to afford a high discharge voltage plateau near ≈4 V with up to ≈1000 mAh g−1 capacity for SCl2/S2Cl2 reduction and up to ≈4000 mAh g−1 capacity at ≈3.1 V plateau for Cl2 reduction. This work reports a −80 °C ≈4.0 V rechargeable lithium/chlorine battery with a 1200–5000 mAh g−1 reversible capacity over up to 130 cycles, employing the newly engineered porous carbon cathode and SOCl2‐based electrolyte. X‐ray spectroscopy and mass spectrometry reveal the highly reversible LiCl/Cl2 redox reactions and trapping mechanism of reactive species at −40 °C to −80 °C.