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•CMC-Li aerogel with 98.4% porosity works as robust support for PEO films.•The electrolyte has a low melting point (30.43 °C) and high strength (3.85 MPa).•Li+ conductivity, transference number, and electrochemical window are enhanced.•Li//LiFePO4 full cells offer a high capacity of 142.2 mAh g−1 for 150 cycles.
Highly porous carboxymethyl cellulose lithium (CMC-Li) aerogel frameworks are used as a novel, robust, high-conductivity support for PEO-based electrolytes, offering a low melting point (30.43 °C) and high tensile strength (3.85 Mpa). The ionic conductivity, Li+ ion transference number, and electrochemical window at 30 °C are 2.59 × 10−4 S cm−1, 0.646, and 5.3 V, respectively.