title: High-Capacitance Mechanism for Ti3C2TxMXene by in Situ Electrochemical Raman Spectroscopy Investigation.
abstract: MXenes represent an emerging family of conductive two-dimensional materials. Their representative, Ti3C2Tx, has been recognized as an outstanding member in the field of electrochemical energy storage. However, an in-depth understanding of fundamental processes responsible for the superior capacitance of Ti3C2TxMXene in acidic electrolytes is lacking. Here, to understand the mechanism of capacitance in Ti3C2TxMXene, we studied electrochemically the charge/discharge processes of Ti3C2Txelectrodes in sulfate ion-containing aqueous electrolytes with three different cations, coupled with in situ Raman spectroscopy. It is demonstrated that hydronium in the H2SO4electrolyte bonds with the terminal O in the negative electrode upon discharging while debonding occurs upon charging. Correspondingly, the reversible bonding/debonding changes the valence state of Ti element in the MXene, giving rise to the pseudocapacitance in the acidic electrolyte. In stark contrast, only electric double layer capacitance is recognized in the other electrolytes of (NH4)2SO4or MgSO4. The charge storage ways also differ: ion exchange dominates in H2SO4, while counterion adsorption in the rest. Hydronium that is characterized by smaller hydration radius and less charge is the most mobile among the three cations, facilitating it more kinetically accommodated on the deep adsorption sites between the MXene layers. The two key factors, i.e., surface functional group-involved bonding/debonding-induced pseudocapacitance, and ion exchange-featured charge storage, simultaneously contribute to the superior capacitance of Ti3C2TxMXene in acidic electrolytes.
authors.affiliation: Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences , Shenyang 110016, China.|School of Materials Science and Engineering, University of Science and Technology of China , Hefei 230026, China.
authors.forename: Minmin
authors.initials: M
authors.lastname: Hu
authors.affiliation: Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences , Shenyang 110016, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
authors.forename: Zhaojin
authors.initials: Z
authors.lastname: Li
authors.affiliation: Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences , Shenyang 110016, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
authors.forename: Tao
authors.initials: T
authors.lastname: Hu
authors.affiliation: Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences , Shenyang 110016, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
authors.forename: Shihao
authors.initials: S
authors.lastname: Zhu
authors.affiliation: Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences , Shenyang 110016, China.
authors.forename: Chao
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences , Shenyang 110016, China.
authors.forename: Xiaohui
authors.identifier: 0000-0001-7271-2662
authors.initials: X
authors.lastname: Wang
keywords: MXene; charging mechanism; electrochemical capacitor; in situ Raman spectroscopy; pseudocapacitance; supercapacitor; two-dimensional materials