Self-standing carbon fiber electrodes hold promise for solid-state battery technology owing to their networked structures improving interparticle connectivity, robustness contributing to mechanical integrity, and surface sites confining Li dendrites. We here evaluate carbonized 3D electrospun fibers filled with polymer electrolytes as anodes in solid-state lithium half cells. Microscopic analysis of the cells demonstrates the high wettability of carbon fibers with electrolytes, promoting an intimate contact between electrolytes and fibers. Solid-state cells delivered high initial capacities up to ∼300 mAh g−1, although the latter cycles were characterized by gradual capacity fade (∼100 mAh g−1 in the 100th cycle with nearly 100% coulombic efficiency), attributed to the onset of parasitic reactions increasing the cell resistance and polarization. When these were benchmarked against similar cells but with the liquid electrolyte, it was found that Li storage in these fiber electrodes is intermediate between graphite and hard carbon in terms of lithiation voltage (vs Li/Li+), corroborating with the nature of carbon assessed by XRD and Raman analysis. These observations can contribute to further development and optimization of solid-state batteries with 3D electrospun carbon fiber electrodes.
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