Lithium ion batteries (LIBs) use Li metal as the anode to increase energy density,becoming an attractive tendency during the development of energy storage systems in recent years. However, their performance is confined by uncontrolled Li dendrite growth. Solid polymer electrolytes (SPEs) become an effective alternative to commercial liquid electrolytes in limiting the growth of Li dendrite by their natural solidity. Moreover, Li ion diffusivity and mobility of the counter anions in SPE are the prerequisite influential factors in LMB performance. These characteristics are assessed by ionic conductivity and lithium transference number. Herein, we build up a concept of SPE by incorporating a porous PVdF-HFP skeleton with a cross-linked polymer electrolyte (NSPE). This modified SPE membrane with high mechanical modulus, named as P-NSPE. P-NSPE presents an acceptable conductivity of 1.11 × 10-4 Scm-1 at 30 oC and improved lithium transference number of 0.45, since NSPE act as the ion transport carrier and PVdF-HFP porous framework act as the efficient pathways for lithium ion diffusion. Besides that, the excellent interfacial stability against the lithium metal electrode, indicating highly stable lithium plating/stripping reversibility and the significantly suppressed Li dendrite growth. The impressed cycling performance of the Li/P-NSPE/LFP cells has resulted from the restriction of lithium dendrite propagation. The battery retains 83% of discharge capacity after 200 cycles under 0.06 mA cm-2 at 30 oC.

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