Asymmetric Structure Design of Electrolytes with Flexibility and Lithium Dendrite-Suppression Ability for Solid-State Lithium Batteries

Solid polymer electrolytes can be used to construct solid-state lithium batteries (SSLBs) using lithium metals as the anode. However, the lifespan and safety problems of SSLBs caused by lithium dendrite growth have hindered their practical application. Here, we have designed and prepared a rigid-flexible asymmetric solid electrolyte (ASE) that is used in building SSLBs. The ASE can inhibit efficiently the growth of lithium dendrites and lead to a long cycle life of SSLBs due to the hierarchical structure of a combination of “polymer-in-ceramic” (i.e., rigid ceramic layer of Li6.4La3Zr1.4Ta0.6O12) and “LiBOB-in-polymer” (i.e., soft polymer-layer of polyethylene oxide and LiBOB components). The results demonstrated that a symmetrical battery with ASE (Li|ASE|Li) can be steadily cycled for more than 2000 h and yielded a flat plating/stripping voltage profile under a current density of 0.1 mA cm–2. As a consequence, the SSLB of LiFePO4|ASE|Li delivered a specific capacity of 155.1 mA h g–1 with a capacity retention rate up to 90.2% after 200 cycles with the Coulombic efficiency over 99.6% per cycle. This asymmetric structure combines the advantages of ceramics and polymers, providing an ingenious solution for building rigid and flexible solid electrolytes.