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Herein, a flexible ceramic/polymer HSE is prepared via in situ coupling reaction. Ceramic and polymer tend to be closely combined by powerful chemical bonds, hence the problem of user interface compatibility is settled plus the ions can transfer rapidly by an expressway. The as-prepared membrane layer demonstrates an ionic conductivity of 9.83 × 10-4 S cm-1 at room-temperature and a high Li+ transference amounts of 0.68. This in situ coupling reaction method provides a good way to resolve the issue of