Recent success in extending the electrochemical stability window of aqueous electrolytes to 3.0 V by using 21 mol kg-1 “water-in-salt” (WiS) has raised a high expectation for developing safe aqueous Li-ion batteries. However, the most compatible Li4Ti5O12 anodes still cannot use WiS electrolyte due to the cathodic limit (1.9 V vs. Li/Li+). Herein, a UV-curable hydrophilic polymer is introduced to further extend the cathodic limit of WiS electrolytes and replace the separator. In addition, a localized strongly basic solid polymer electrolyte (SPE) layer is coated on the anode to promote the formation of an LiF-rich SEI. The synthetic impacts of UV-crosslinking and local alkaline SPE on the anodes extend the electrochemical stability window of the solid-state aqueous polymer electrolyte to ∼3.86 V even at a reduced salt concentration of 12 mol kg−1. It enables a separator-free LiMn2O4//Li4Ti5O12 aqueous full cell with a practical capacity ratio (P/N = 1.14) of the cathode and anode to deliver a steady energy density of 151 W h kg−1 at 0.5C with an initial Coulombic efficiency of 90.50% and cycled for over 600 cycles with an average Coulombic efficiency of 99.97%, which has never been reported before for an aqueous LiMn2O4//Li4Ti5O12 full cell. This flexible and long-duration aqueous Li-ion battery with hydrogel WiSE can be widely used as a power source in wearable devices and electrical transportations where both energy density and battery safety are of high priority. An ultra-thick LTO electrode with UV-curable polymer electrolyte as the binder is demonstrated as a solid state battery electrode. And a high-voltage (7.4 V) solid-state bipolar cell is assembled with a solid-state UV-curable polymer as the electrolyte.
