Journal
ACS NANO
Volume 10, Issue 12, Pages 11344-11350Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.6b06597
Keywords
MXene; two-dimensional materials; in situ Raman spectroscopy; charging mechanism; pseudocapacitance; supercapacitor; electrochemical capacitor
Categories
Funding
- Chinese Academy of Sciences (CAS)
- Shenyang National Laboratory for Materials Science, Institute of Metal Research, CAS
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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 Ti3C2Tx MXene in acidic electrolytes is lacking. Here, to understand the mechanism of capacitance in Ti3C2Tx MXene, we studied electrochemically the charge/discharge processes of Ti3C2Tx electrodes in sulfate ion-containing aqueous electrolytes with three different cations, coupled with in situ Raman spectroscopy. It is demonstrated that hydronium in the H2SO4 electrolyte 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)(2)SO4 or 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 Ti3C2Tx MXene in acidic electrolytes.
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