An Ultrafast-Charging Daniell-Type All-Solid-State Battery.

All-solid-state batteries (ASSBs) demonstrate unique advantages in energy density and safety performance. However, the point contact between multiphase particles restricts the ion/electron transport, severely limiting the kinetic performance of ASSBs. Planar metal electrodes can cancel out tortuous transport paths, providing the possibility for a revolutionary breakthrough in the kinetic performance of ASSBs. Herein, we develop a universal electrolyte framework that enables the comigration of Li+ and Cu+, facilitating the design of a Daniell-type ASSB. Remarkably, this system exhibits unprecedented kinetic performance and cycling stability. By canceling out the tortuous ion/electron transport, 100% capacity retention is achieved even under a 10-fold increment of current density (from 1.0 to 10.0 mA cm-2). Meanwhile, the reduction in the average discharge voltage is also extremely small (ΔV ≈ 45 mV). The invariant interfacial microstructure ensures 100% capacity retention over 10,000 cycles at 10.0 mA cm-2 (30 °C) and 25,000 cycles at 100.0 mA cm-2 (60 °C). The metal electrode configuration further endows exceptional advantages in electrode fabrication and battery recycling, reducing material costs by 80% and recycling costs by 97% compared to traditional ASSBs. This work transcends the cognitive constraints of powder-based cathodes, charting a transformative pathway for high-performance energy storage systems.