Mechano‐Electrochemically Promoting Lithium Atom Diffusion and Relieving Accumulative Stress for Deep‐Cycling Lithium Metal Anodes

Abstract Lithium metal batteries (LMBs) can double the energy density of lithium‐ion batteries. However, the notorious lithium dendrite growth and large volume change are not well addressed, especially under deep cycling. Here, an in–situ mechanical–electrochemical coupling system is built, and it is found that tensile stress can induce smooth lithium deposition. Density functional theory (DFT) calculation and finite element method (FEM) simulation confirm that the lithium atom diffusion energy barrier can be reduced when the lithium foils are under tensile strain. Then tensile stress is incorporated into lithium metal anodes by designing an adhesive copolymer layer attached to lithium in which the copolymer thinning can yield tensile stress to the lithium foil. Elastic lithium metal anode (ELMA) is further prepared via introducing a 3D elastic conductive polyurethane (CPU) host for the copolymer–lithium bilayer to release accumulated internal stresses and resist volume variation. The ELMA can withstand hundreds of compression‐release cycles under 10% strain. LMBs paired with ELMA and LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode can operate beyond 250 cycles with 80% capacity retention under practical condition of 4 mAh cm⁻² cathode capacity, 2.86 g Ah⁻¹ electrolyte‐to‐capacity ratio (E/C) and 1.8 negative‐to‐cathode capacity ratio (N/P), five times of the lifetime using lithium foils.