Operating High‐Energy Lithium‐Metal Pouch Cells with Reduced Stack Pressure Through a Rational Lithium‐Host Design

Abstract Transitioning from a liquid electrolyte to an inorganic solid electrolyte offers a potential pathway to enable highly reversible lithium‐metal anodes. However, the solid‐electrolyte‐protected lithium‐metal anode suffers from poor interfacial ionic contacts and requires an impractically high stack pressure ( > 1.0 MPa) to maintain the interfacial contacts. It is demonstrated here that combining a hollow silver/carbon fiber scaffold and an inorganic/organic composite electrolyte enables a highly reversible lithium‐metal anode. Since the high surface area of the electrode provides intimate contact and the hollow structure of the electrode relieves the lithium plating‐induced stress, the electrode/electrolyte interface remains stable during cycling even under mild stack pressure. This unconventional structural design is validated in practical pouch cells assembled with the 3D lithium host containing a onefold excess of lithium and a high‐nickel cathode. At a mild stack pressure of 320 kPa, the pouch cell displays 83% capacity retention for 200 cycles. The work illustrates that combining a hollow electrode architecture and a robust solid electrolyte offers a practical pathway toward rechargeable lithium‐metal anodes.