Journal Article

Li+(ionophore) nanoclusters engineered aqueous/non-aqueous biphasic electrolyte solutions for high-potential lithium-based batteries

Wang, Chunsheng, Chen, Fu, Zhang, Nan, Tan, Sha, Liu, Yijie, Phan, An L., Borodin, Oleg, Zhang, Weiran, Zhang, Xiyue, Pollard, Travis P., Yang, Chongyin, Yang, Xiao-Qing, Xu, Jijian, Hu, Enyuan

2025

Overview

The use of aqueous/non-aqueous biphasic electrolyte solutions in Li-based battery systems circumvents the limitations of poor reductive stability of aqueous electrolyte solutions, broadening their electrochemical stability window. However, aqueous/non-aqueous electrolytes suffer from biphasic mixing and high impedance when Li ions cross the biphasic interface. Here we propose the use of 12-crown-4 (12C4) and tetraglyme (G4) as lithium ionophores to form Li + (ionophore) nanoclusters in both non-aqueous and aqueous phases to overcome the interface challenges in biphasic electrolytes. The Li + (ionophore) nanoclusters have the H 2 O-excluding inner Li + solvation structure in non-polar 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), allowing fast charge transport across the biphasic interface without solvent mixing or water shuttling. A tailored electrolyte formulation comprising the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, 12C4, TTE and H 2 O solvents (labelled LiTFSI−12C4@TTE/H 2 O) demonstrates low impedance (2.7 Ω cm − 2 ) at the TTE/H 2 O interface and enabling 2,000 cycles of prelithiated graphite||LiFePO 4 coin cells at 850 mA g −1 with an average Coulombic efficiency of 99.8%. Single-layer 22.5 mAh Li||LiMn 2 O 4 pouch cells using LiTFSI−12C4@TTE/H 2 O electrolyte with G4 delivered a stable discharge capacity of about 1.3 mAh cm −2 for 80 cycles at 0.5 mA cm −2 . Aqueous and non-aqueous Li-based electrolyte solutions have narrow electrochemical stability windows, which hinder the operation of batteries at high cell potentials. Here, to circumvent this limitation, the authors propose the combined use of tailored aqueous and non-aqueous electrolyte solutions in various Li-based cell configurations.

• Publisher: Nature Publishing Group UK,Nature Publishing Group
• Subject: 119/118 / 140/131 / 140/133 / 140/146 / 142/136 / 639/301/299 / 639/4077/4079 / 639/4077/4079/891 / 639/638/161 / Aqueous electrolytes / Charge transport / Chemistry and Materials Science / Discharge capacity / Electrochemistry / Electrodes / Electrolytes / Electrolytic cells / ENERGY STORAGE / High impedance / Impedance / Ionophores / Lithium / Lithium batteries / Lithium manganese oxides / Materials Science / Nanoclusters / Nanotechnology / Nanotechnology and Microengineering / NMR / Nonaqueous electrolytes / Nuclear magnetic resonance / Simulation / Solvation / Solvents / Spectrum analysis / Stability / Water