Polymeric single lithium (Li)-ion conductors (SICs), along with inorganic conducting materials such as sulfides and oxides, have received significant attention as promising solid-state electrolytes. Yet their practical applications have been plagued predominantly by sluggish ion transport. Here, a new class of quasi-solid-state SICs based on anion-rectifying semi-interpenetrating polymer networks (semi-IPNs) with reticulated ion nanochannels are demonstrated. This semi-IPN SIC (denoted as sSIC) features a bicontinuous and nanophase-separated linear cationic polyurethane (cPU), which supports single-ion conducting nanochannels, and ultraviolet-crosslinked triacrylate polymer, which serves as a mechanical framework. The cPU phase is preferentially swollen with a liquid electrolyte and subsequently allows anionrectifying capability and nanofluidic transport via surface charge, which enable fast Li + migration through ion nanochannels. Such facile Li + conduction is further enhanced by tuning ion-pair (i.e., freely movable anions and cations tethered to the cPU chains) interaction. Notably, the resulting sSIC provides high Li + conductivity that exceeds those of commercial carbonate liquid electrolytes. This unusual single-ion conduction behavior of the sSIC suppresses anion-triggered interfacial side reactions with Li-metal anodes and facilitates electrochemical reaction kinetics at electrodes, eventually improving rate performance and cycling retention of Li-metal cells (comprising LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes and Li-metal anodes) compared to those based on carbonate liquid electrolytes.

Despite the enormous potential of aqueous zinc (Zn)‐ion batteries as a cost‐competitive and safer power source, their practical applications have been plagued by the chemical/electrochemical instability of Zn anodes with aqueous electrolytes. Here, ionic liquid (IL) skinny gels are reported as a new class of water‐repellent ion‐conducting protective layers customized for Zn anodes. The IL skinny gel (thickness ≈500 nm), consisting of hydrophobic IL solvent, Zn salts, and thiol‐ene polymer compliant skeleton, prevents the access of water molecules to Zn anodes while allowing Zn2+ conduction for redox reactions. The IL‐gel‐skinned Zn anode enables sustainable Zn plating/stripping cyclability under 90% depth of discharge (DODZn) without suffering from water‐triggered interfacial parasitic reactions. Driven by these advantageous effects, a Zn‐ion full cell (IL‐gel‐skinned Zn‐anode||aqueous‐electrolyte‐containing MnO2 cathode) exhibits high charge/discharge cycling performance (capacity retention ≈95.7% after 600 cycles) that lies beyond those achievable with conventional aqueous Zn‐ion battery technologies.

Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi0.8Co0.1Mn0.1O2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm−2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg−1 and 772 Wh L−1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm−2) and 25 °C.

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