Despite the continuous progress in the research and development of Ti 3 C 2 T x (MXene) electrodes for high-power batteries and supercapacitor applications, the role of the anions in the electrochemical energy storage and their ability to intercalate between the MXene sheets upon application of positive voltage have not been clarified. A decade after the discovery of MXenes, the information about the possibility of anion insertion into the restacked MXene electrode is still being questioned. Since the positive potential stability range in diluted aqueous electrolytes is severely limited by anodic oxidation of the Ti, the possibility of anion insertion was evaluated in concentrated aqueous electrolyte solutions and aprotic electrolytes as well. To address this issue, we have conducted in situ gravimetric electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) measurements in highly concentrated LiCl and LiBr electrolytes, which enable a significant extension of the operation range of the MXene electrodes toward positive potentials. Also, halogens are among the smallest anions and should be easier to intercalate between MXene layers, in comparison to multiatomic anions. On the basis of mass change variations in the positive voltage range and complementary density functional theory calculations, it was demonstrated that insertion of anionic species into MXene, within the range of potentials of interest for capacitive energy storage, is not likely to occur. This can be explained by the strong negative charge on Ti 3 C 2 T x sheets terminated by functional groups.

Among the examined organic electrodes for aqueous mono and multivalent ions batteries, polyimide is considered a promising candidate because of its high capacity and good cyclability in different electrolyte solutions. While most of the studies so far were focused on the energetic performance of polyimide anodes, much less is known about their charge storage mechanism and particularly how such electrodes are affected by the solvation properties of the inserted cations. Using in situ EQCM-D, a direct assessment of the cationic fluxes and their hydration shells inserted/extracted to/from PI electrodes upon potential application was performed for a large variety of mono and multivalent cations. Our observations demonstrated a pronounced withdrawal of water molecules from the polymeric electrodes during insertion of chaotropic cations and significantly less water withdrawal upon insertion of kosmotropic cations. These findings are well correlated with the capacity and the rate capability of the polyimide electrodes in the examined systems and shed light on their charge storage mechanism.

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