Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries

[Image: see text] The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO(2) (LCO) using a moderate concentration of 0.5∼3 mol kg(–1) lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li(+), showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li(+) helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI(–))) and explained better galvanostatic cyclability in LCO cells.