Ma Huige, Yang Mingsheng, Li Rui, Zheng Liping, Hao Yuxin, Li Hongwei, Li Mengxiao, Zhao Guoqing, Wang Zhihui, Wang Bei, Hu Mingjun, Yang Jun
Beijing Institute of Nanoenergy & Nanosystems, Chinese Academy of Sciences, Beijing, 101400, China.
School of Nanoscience and Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China.
Small. 2025 Apr;21(14):e2405004. doi: 10.1002/smll.202405004. Epub 2024 Oct 6.
The broad applications of rechargeable batteries urge people to develop alternative energy storage devices with sustainable resources, high capacity, long cycling life, and wide-temperature operability. Aqueous proton batteries are considered as a state-of-the-art energy storage system due to their intrinsic safety and low cost. However, aqueous electrolytes have a low boiling point and narrow electrochemical stability window, limiting their applications in wide-temperature and high-energy batteries. Herein, a hybrid organic ionic liquid electrolyte with organic alkali 1-methyl-1,2,4-triazole (MTA) protonated by organic acid bis(trifluoromethysulfonyl)imide (HTFSI) as proton carriers and tetramethylene sulfone (TMS) as the solvent, noted as HTFSI-MTA-TMS, exhibited the stable electrochemical windows exceeding 5 V at -20 °C and 3.5 V at 80 °C. Benefiting from this electrolyte, the assembled MnO-S//MoO button proton full battery can display an operation voltage up to 1.8 V, energy density of 44.8 Wh kg, and good cycling stability at room temperature when bis(trifluoromethanesulfonyl)imide manganese (II) salt (Mn(TFSI)) is introduced into the electrolyte, and run well in a wide-temperature range (-20 °C-60 °C). The work reveals the potential of organic acid-alkali coregulated electrolytes to meet the need of energy storage in a wide-temperature range and will advance the development of high-energy proton batteries.
可充电电池的广泛应用促使人们开发具有可持续资源、高容量、长循环寿命和宽温度可操作性的替代储能设备。水系质子电池因其本质安全性和低成本而被视为一种先进的储能系统。然而，水系电解质沸点低且电化学稳定性窗口窄，限制了它们在宽温度和高能量电池中的应用。在此，一种混合有机离子液体电解质，以有机酸双（三氟甲基磺酰）亚胺（HTFSI）质子化的有机碱1-甲基-1,2,4-三唑（MTA）作为质子载体，四亚甲基砜（TMS）作为溶剂，记为HTFSI-MTA-TMS，在-20℃时表现出超过5V的稳定电化学窗口，在80℃时为3.5V。受益于这种电解质，当将双（三氟甲磺酰）亚胺锰（II）盐（Mn（TFSI））引入电解质时，组装的MnO-S//MoO纽扣质子全电池在室温下可显示高达1.8V的工作电压、44.8Wh kg的能量密度和良好的循环稳定性，并在宽温度范围（-20℃-60℃）内运行良好。这项工作揭示了有机酸碱协同调控电解质满足宽温度范围储能需求的潜力，并将推动高能质子电池的发展。
