Fundamental Understanding and Quantification of Capacity Losses Involving the Negative Electrode in Sodium-Ion Batteries

Knowledge about capacity losses related to the solid electrolyte interphase (SEI) in sodium-ion batteries (SIBs) is still limited. One major challenge in SIBs is that the solubility of SEI species in liquid electrolytes is comparatively higher than the corresponding species formed in Li-ion batteries. This study sheds new light on the associated capacity losses due to initial SEI formation, SEI dissolution and subsequent SEI reformation, charge leakage via SEI and subsequent SEI growth, and diffusion-controlled sodium trapping in electrode particles. By using a variety of electrochemical cycling protocols, synchrotron-based X-ray photoelectron spectroscopy (XPS), gas chromatography coupled with mass spectrometry (GC-MS), and proton nuclear magnetic resonance (1H-NMR) spectroscopy, capacity losses due to changes in the SEI layer during different open circuit pause times are investigated in nine different electrolyte solutions. It is shown that the amount of capacity lost depends on the interplay between the electrolyte chemistry and the thickness and stability of the SEI layer. The highest capacity loss is measured in NaPF6 in ethylene carboante mixed with diethylene carbonate electrolyte (i.e., 5 mu Ah h-1/2pause or 2.78 mAh g center dot h-1/2pause) while the lowest value is found in NaTFSI in ethylene carbonate mixed with dimethoxyethance electrolyte (i.e., 1.3 mu Ah h-1/2pause or 0.72 mAh g center dot h-1/2pause). A detailed quantification of different aging mechanisms related to electrolyte solution and negative electrode is presented in this study. The dissolution of solid electrolyte interphase (SEI), diffusion-controlled ion trapping, continuous SEI dissolution and reformation, and chemical desodiation and SEI growth in sodium-ion batteries are discussed here using a variety of analytical tools.image