Abstract
Knowledge about capacity losses due to the formation and dissolution of the solid electrolyte interphase (SEI) layer in sodium-ion batteries (SIBs) is still limited. One major challenge in SIBs is the fact that the SEI generally contains more soluble species than the corresponding SEI layers formed in Li-ion batteries. By cycling carbon black electrodes against Na-metal electrodes, to mimic the SEI formation on negative SIB electrodes, this study studies the associated capacity losses in different carbonate electrolyte systems. Using electrochemical testing and synchrotron-based X-ray photoelectron (XPS) experiments, the capacity losses due to changes in the SEI layer and diffusion of sodium in the carbon black electrodes during open circuit pauses of 50 h, 30 h, 15 h and 5 h are investigated in nine different electrolyte systems. The different contributions to the open circuit capacity loss were determined using a new approach involving different galvanostatic cycling protocols. It is shown that the capacity loss depends on the interplay between the electrolyte chemistry and the thickness and stability of the SEI layer. The results show, that the Na-diffusion into the bulk electrode gives rise to a larger capacity loss than the SEI dissolution. Hence, Na-trapping effect is one of the major contribution in the observed capacity losses. Furthermore, the SEI formed in NaPF6-EC:DEC was found to become slightly thicker during 50 h pause, due to self-diffused deintercalation of Na from the carbon black structure coupled by further electrolyte reduction. On the other hand, the SEI in NaTFSI with the same solvent goes into dissolution during pause. The highest SEI dissolution rate and capacity loss was observed in NaPF6-EC:DEC (0.57 μAh/hpause) and the lowest in NaTFSI-EC:DME (0.15 μAh/hpause).
The use of protic ionic liquids with cathodes for sodium-ion batteries