Swallowing Lithium Dendrites in All‐Solid‐State Battery by Lithiation with Silicon Nanoparticles

Eliminating the uncontrolled growth of Li dendrite inside solid electrolytes is a critical tactic for the performance improvement of all‐solid‐state Li batteries (ASSLBs). Herein, a strategy to swallow and anchor Li dendrites by filling Si nanoparticles into the solid electrolytes by the lithiation effect with Li dendrites is proposed. It is found that Si nanoparticles can lithiate with the adjacent Li dendrites which have a strong electron transport ability. Such effect can inhibit the formation of Li dendrites at the interface of Li anode, and also swallow the tip Li inside the solid electrolytes, and thus inhibiting its longitudinal growth and avoiding the solid electrolyte puncturing. As a proof of concept, a novel sandwich‐structure solid electrolyte of Li(6.7)La(3)Zr(2)Al(0.1)O(12) (LLZA)‐PEO/Si‐PEO electrolyte/ (LLZA)‐PEO with asymmetrical structure is first constructed and demonstrated stable Li plating/stripping over 1800 h and remarkably improved cycling stability in Li/LiFePO(4) cells with a reversible capacity of 111.9 mAh g(−1) at 1 C after 150 cycles. The proof of lithiation of Si‐PEO electrolyte in the interlayer is also verified. Furthermore, the pouch cell thus prepared exhibits comparable cyclic stability and is allowable for folding and cutting, suggesting its promising application in ASSLBs by this simple and efficient strategy.