Silver exsolution from Li-argyrodite electrolytes for initially anode-free all-solid-state batteries

作者：S. Choi, Chang Hoon Baek, Jihoon Oh, Geung-Jong Lee, Minsoo Kim, Hyesu Lee, Dong-Joo Yoo, Y. Jung, Kyungsu Kim, Ji-Sang Yu, Woosuk Cho, Haesun Park, Jang Wook Choi · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-61074-9 · 被引用次数：22 · 研究领域：Medicine

Achieving stable cyclability in initially anode-free all-solid-state batteries is challenging due to non-uniform Li (de)plating, especially under practical operating conditions. Here, we introduce a bilayer comprising a silver(Ag)-doped Li-argyrodite electrolyte layer in contact with the undoped Li-argyrodite electrolyte. During charging, electrochemical exsolution of Ag+ from the silver-doped Li argyrodite forms nanoscale, lithiophilic silver seeds along grain boundaries and in pores where they are accessible for electron transfer. These silver seeds alloy with Li to induce uniform Li plating underneath and return to the electrolyte layer upon Li stripping to enhance the reversibility during cycling. With silver exsolution, a pouch-type full-cell with a volumetric energy density of 1312 Wh L−1 (excluding the packaging materials) and areal discharge capacity of 7.0 mAh cm−2 at 0.7 mA cm−2, demonstrated stable cycling at a practical stack pressure of 2.0 MPa. This study highlights that Ag+ diffusion in the Li-argyrodite solid electrolyte and its electrochemical exsolution are an effective strategy for robust, high-energy-density initially anode-free all-solid-state batteries. Achieving uniform Li plating in solid-state batteries is key for their practical application. Here, the authors integrate a silver-doped lithium argyrodite layer in initially anode-free all-solid-state batteries, promoting uniform lithium plating and cell operation under a low stack pressure of 2 MPa thro...