Degradation processes of carbon negative electrodes for all-solid lithium polymer batteries were investigated using X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and Scanning Electron Microscope (SEM). The cycling performances of the electrodes are significantly affected by the mixing speed of the electrode slurry. The cross-sectional SEM images of the electrodes containing vapor-grown carbon fiber (VGCF) show that more voids remained in the electrodes, if the slurry was mixed at high speed. The voids in the composite electrode expand and increase during the cycling test of the cell resulting in the capacity fading. On the other hand, the electrodes containing carbon nanotubes (CNT) show an opposite trend, because the high mixing speed improves the dispersibility of the CNT resulting in the formation of the less voids in the electrode. The electrode containing both VGCF and CNT prepared at high mixing speed shows the best cycleability among all the electrodes. In spite of some voids initially form in the electrode, the CNT seems to have prevented further increase and expansion of the voids.