The pursuit of energy-efficient for electric vehicles and aircraft has driven the exploration of structural batteries. In the material-level design of structural batteries, electrode and electrolyte materials act as both load-bearing structures and energy storage elements. During these developments, carbon fibers with excellent mechanical and electrical conductive properties were used as electroactive materials and current collectors. However, most of these systems are combined with electrolytes without mechanical integrity (such as liquid or gel-type electrolytes), thus limiting the load-carrying performance of the battery. Currently the development of electrolytes for structural batteries remains challenging because the parameters enhancing electrochemical properties are often in contradiction with that for mechanical properties. In response to this challenge, the present study proposes a multifunctional composite electrolyte with balanced mechanical and electrochemical properties, which uses polyvinylidene fluoride (PVDF) as the matrix and metal-organic frameworks (MOF) modified glass fabric (MOF@GF) as the reinforcement. This study systematically investigates the following factors on mechanical and electrochemical properties of the composite electrolytes. Firstly, MOF with high specific surface areas and metal open sites onto the surface of glass fibers establishes a robust ion transporting network. With 20% MOF modified glass fiber and resin content 89%, the electrolyte exhibits high ion conductivity (1.74 × 10-3 S cm−1). In addition, by carefully controlling the resin content, a key parameter for fiber-reinforced composites, a delicate balance between mechanical strength and ionic conductivity can be achieved. Furthermore, interfaces were investigated, including glass fiber-MOF and MOF-PVDF interfaces, revealing the importance of effectively transfers stress and maintains structural integrity. Finally, these findings were combined to create a structural lithium metal battery that utilizes carbon fiber (CF) as the positive electrode and lithium metal as the anode. The resulting battery exhibits ultra-high tensile strength while maintaining a moderate capacity, ensuring normal operation under high voltage stress. This breakthrough discovery not only enhances the understanding of multifunctional composite electrolytes, but is also expected to promote further research and applications in the field of structural batteries. The promise of enhanced system electrolytes opens new avenues for lightweight design, space efficiency and expanded energy storage capabilities in electric vehicles and aircraft. Figure 1 . SEM images of (a) bare glass fiber. (b) MOF grown in-situ on glass fiber. (c) Single fiberglass within polymer matrix. (d) Cross section of the composite polymer electrolyte membrane. Figure 1
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