Ion-Conductive Wires Form High-Performance All-Solid-State Polymer Electrolytes

Solid-state batteries are poised to transform energy storage by eliminating the risks of flammable liquid electrolytes, enabling safer, higher-density systems for electric vehicles, renewable grids, and electronics in the race to net-zero emissions by 2050. Yet, all-solid-state polymer electrolytes have been limited by low ionic conductivity, poor lithium transference, and instability at room temperature, often requiring additives or heating that compromise their advantages. We introduce ion-conductive wires (ICWs), a new class of self-assembling nanostructured polymers with a hierarchical block-brush architecture. Featuring a flexible polysiloxane backbone, a PEG-rich core for rapid anisotropic Li+ transport, and a fluorinated sheath for oxidative stability and anion suppression, ICWs self-organize with continuous channels via the fluorous effect. Screening a library of architectures revealed an optimal design delivering an ionic conductivity of 1.8 × 10–4 S cm–1, a lithium transference number of 0.62, and stability up to 5.23 V at 30 °C─without liquids or fillers. This enables 200 cycles in Li/LFP cells with 96% capacity retention, stable operation in high-voltage Li/NCM622 cells, and 2000 h of lithium plating/stripping. ICWs offer a tunable platform for high-performance, scalable solid-state batteries, accelerating sustainable energy solutions.