AbstractThe continuously increasing number and size of lithium-based batteries developed for large-scale applications raise serious environmental concerns. Herein, we address the issues related to electrolyte toxicity and safety by proposing a “water-in-ionomer” type of electrolyte which replaces organic solvents by water and expensive and toxic fluorinated lithium salts by a non-fluorinated, inexpensive and non-toxic superabsorbing ionomer, lithium polyacrylate. Interestingly, the electrochemical stability window of this electrolyte is extended greatly, even for high water contents. Particularly, the gel with 50 wt% ionomer exhibits an electrochemical stability window of 2.6 V vs. platinum and a conductivity of 6.5 mS cm⁻¹ at 20 °C. Structural investigations suggest that the electrolytes locally self-organize and most likely switch local structures with the change of water content, leading to a 50% gel with good conductivity and elastic properties. A LiTi₂(PO₄)₃/LiMn₂O₄ lithium-ion cell incorporating this electrolyte provided an average discharge voltage > 1.5 V and a specific energy of 77 Wh kg⁻¹, while for an alternative cell chemistry, i.e., TiO₂/LiMn₂O₄, a further enhanced average output voltage of 2.1 V and an initial specific energy of 124.2 Wh kg⁻¹ are achieved.