Molecular-Scale Interaction between Sub-1 nm Cluster Chains and Polymer for High-Performance Solid Electrolyte

Organic-inorganic interface in composite solid electrolyte could lead to increased ion transport for solid-state lithium batteries; however, most inorganic fillers have much larger size than polymer chains, which results in severe aggregation of inorganic fillers and poor ionic conductivity. Herein, functional sub-1nm inorganic cluster chains were integrated with polymer chains to fabricate composite solid electrolyte with enhanced ionic conductivity. Different from all other inorganic fillers, the sub-1nm inorganic cluster chains with diameter <1 nm have similar size and geometry compared with polymer chains, exhibiting polymer-like solution properties. A transparent sub-1nm inorganic filler/polymer mixed solution was generated to realize monodispersion of cluster chains as functional fillers in polymer matrix. Meanwhile, abundant oxygen vacancies on cluster chains interact with polymer chains and lithium salts at molecular-scale, which decreases the complexation of polymer segments with Li+ and promote the dissociation of lithium salts, thereby improving Li+ transport. As a result, the composite solid electrolyte exhibits high ionic conductivity (0.4 mS cm−1) and large mobile Li+ distribution (50.8%). This work pushes the size of nanofillers down to <1 nm, which is a unique approach to the molecular-scale interaction between nanofillers and polymers to boost ion transport in solid electrolytes.