Free-standing and flexible carbon nanofiber membranes (CNMs) with a three-dimensional network structure were fabricated based on PMDA/ODA polyimide by combining electrospinning, imidization, and carbonization strategies. The influence of carbonization temperature on the physical-chemical characteristics of CNMs was investigated in detail. The electrochemical performances of CNMs as free-standing electrodes without any binder or conducting materials for lithium-ion batteries were also discussed. Furthermore, the surface state and internal carbon structure had an important effect on the nitrogen state, electrical conductivity, and wettability of CNMs, and then further affected the electrochemical performances. The CNMs/Li metal half-cells exhibited a satisfying charge-discharge cycle performance and excellent rate performance. They showed that the reversible specific capacity of CNMs carbonized at 700 °C could reach as high as 430 mA h g-1 at 50 mA g-1, and the value of the specific capacity remained at 206 mA h g-1 after 500 cycles at a high current density of 1 A g-1. Overall, the newly developed carbon nanofiber membranes will be a promising candidate for flexible electrodes used in high-power lithium-ion batteries, supercapacitors and sodium-ion batteries.
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