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Widespread commercial adoption of polymer electrolytes for lithium-ion batteries has been hindered by subpar transport properties, namely, ionic conductivities of <1 mS/cm at room temperature and slower Li + compared to anion transport. The developed polymer and water-in-salt electrolyte demonstrated preferential Li + transport compared to the anion via pulsed field gradient NMR, acceptable ionic conductivities of >1 mS/cm at 25 °C, and an extended electrochemical stability window compared to water-in-salt electrolytes. This polymer electrolyte has a flexible liquid/solid transition through polymer molecular weight tuning, and both liquid and solid iterations are investigated. MD simulations provided additional insight into the Li + solvation environment and the mechanism of fast, preferential Li + transport through percolation of water-rich Li + (H 2 O) n nanodomains inside the poly(ethylene oxide) matrix.

As lithium-ion batteries (LIBs) continue to grow in use for energy storage applications, concerns over their safety have influenced research for alternative materials, particularly solid-state electrolytes to replace the highly flammable and electrochemically unstable liquid organic electrolytes used in commercial LIBs. Aqueous-based solid polymer electrolytes (SPEs) offer a safer approach by using water as an abundant, cheap, and non-toxic solvent in an inherently nonflammable polymer matrix. This class of electrolyte also offers decreased cost and weight, ease of processibility, and increased long-term chemical and mechanical stability. However, widespread commercial adoption of SPEs for lithium-ion batteries has been hindered by subpar transport properties, namely, ionic conductivities <1 mS/cm at room temperature and slower Li+ transport compared to anion transport due to slow polymer chain mobility. The use of water as a solvent also lends to restrictive electrochemical stability windows (ESWs) due to its nonideal redox properties that lead to minimal anodic and cathodic limits, dominated by hydrogen evolution at potentials beyond common anode materials (>2 V vs. Li/Li+).To combat these challenges, our work builds upon the concept of super-concentrated salt systems. In the solid-state regime, highly concentrated “polymer-in-salt” systems can exhibit an ion cluster effect allowing for fast cationic transport decoupled from polymer chain segmental motion. In the aqueous regime, highly concentrated “water-in-salt” systems exhibit the formation of a passivating solid electrolyte interphase (SEI) through reduction of TFSI- to form LiF on the anode surface. The presence of water in the “water-in-salt” system also gives rise to a disproportionation of Li+ solvation environments, namely TFSI-rich and water-rich domains, allowing for fast cationic transport through the water domains. By including a highly concentrated “water-in-salt” system into a polymer matrix, the unique aqueous solid polymer-in-salt electrolyte (ASPE) demonstrates preferential Li+ transport compared to anion transport, high ionic conductivity, and extended ESW. This system also exhibits unique stability in air that eliminates the need for meticulously dry environments and solution processing, which is desirable to manufacturers for substantial savings in productions costs.We demonstrate that the ASPE comprised of poly(ethylene oxide) (PEO), water, and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) salt can achieve a high room temperature ionic conductivity of >1.75 mS/cm. Pulsed field gradient NMR shows a lithium transference number of 0.66, which was corroborated with electrochemical impedance spectroscopy. Molecular dynamic simulations reveal that the exceptional transport properties of the ASPE are likely due to decoupling of ion conduction from the polymer-assisted transport seen in typical SPEs, instead being dominated by water-assisted vehicular transport. The system exhibits stability to ~1.5 V vs. Li/Li+, enabling access to anode ma...

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