Abstract

Abstract Flexible solid‐state lithium metal batteries (SSLMBs) are highly desirable for future wearable electronics because of their high energy density and safety. However, flexible SSLMBs face serious challenges not only in regulating the Li plating/stripping behaviors but also in enabling the mechanical flexibility of the cell. Both challenges are largely associated with the interfacial gaps between the solid electrolytes and the electrodes. Here, a UV‐permeable and flexible composited Li metal anode (UVp‐Li), which possesses a unique light‐penetrating interwoven structure similar to textiles is reported. UVp‐Li allows one‐step bonding of the cathode, anode, and solid electrolyte via an in situ UV‐initiated polymerization method to achieve the gapless SSLMBs. The gapless structure not only effectively stabilizes the plating/stripping of Li metal during cycling, but also ensures the integrity of the cell during mechanical bending. UVp‐Li symmetric cell presents a stable cycling over 1000 h at 0.5 mA cm −2 . LiFePO 4 ||UVp‐Li full cells (areal capacity ranging from 0.5 to 3 mAh cm −2 ) show outstanding capacity retention of over 84% after 500 charge/discharge cycles at room temperature. Large pouch cells using high‐loading cathodes maintain stable electrochemical performance during 1000 times of dynamic bending.