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Moreover, the in situ XRD investigation shows a reversible lithium insertion behaviour with a limited volume change.To enhance the compatibility between the polymer-based electrolytes and electrodes, and promote the interfacial ion conduction, a novel approach to engineer the interfaces between all-solid-state composite polymer electrolyte and electrodes using thin layers of ferroelectrics is introduced. The well-designed and ferroelectric-engineered composite polymer electrolyte demonstrates an attractive ionic conductivity of 7.9 × 10