Using MXene as a Chemically Induced Initiator to Construct High-Performance Cathodes for Aqueous Zinc-Ion Batteries.

MXene usually exhibits weak pseudo-capacitance behavior in aqueous zinc-ion batteries, which cannot provide sufficient reversible capacity, resulting in the decline of overall capacity when used as the cathode materials. Taking inspiration from polymer electrolyte engineering, we have conceptualized an in-situ induced growth strategy based on MXene materials. Herein, 5.25 % MXene was introduced into the nucleation and growth process of vanadium oxide (HVO), providing the heterogeneous nucleation site and serving as an initiator to regulate the morphology and structural of vanadium oxide (T-HVO). The resulted materials can significantly improve the capacity and rate performance of zinc-ion batteries. The growth mechanism of T-HVO was demonstrated by both characterizations and DFT simulations, and the improved performance was systematically investigated through a series of in-situ experiments related to dynamic analysis steps. Finally, the evaluation and comparison of various defect introduction strategies revealed the efficient, safety, and high production output characteristics of the in-situ induced growth strategy. This work proposes the concept of in-situ induced growth strategy and discloses the induced chemical mechanism of MXene materials, which will aid the understanding, development, and application of cathode in aqueous zinc-ion batteries.

Mn2+-Doped MoS2/MXene Heterostructure Composites as Cathodes for Aqueous Zinc-Ion Batteries.

Typical layered transition-metal chalcogenide materials, especially MoS2, are gradually attracting widespread attention as aqueous Zn-ion battery (AZIB) cathode materials by virtue of their two-dimensional structure, tunable band gap, and abundant edges. The metastable phase 1T-MoS2 exhibits better electrical conductivity, electrochemical activity, and zinc storage capacity compared to the thermodynamically stable 2H-MoS2. However, 1T-MoS2 is still limited by the phase stability and layered structure destruction for AZIB application. Thus, a three-dimensional interconnected network heterostructure (Mn-MoS2/MXene) consisting of Mn2+-doped MoS2 and MXene with a high percentage of 1T phase (82.9%) was synthesized by hydrothermal methods and investigated as the cathode for AZIBs. It was found that S-Mn-S covalent bonds between MoS2 interlayers and Ti-O-Mo bonds at heterogeneous interfaces can act as "electron bridges" to facilitate electron and charge transfer. And the doping of Mn2+ and the combination of MXene not only expanded the interlayer spacing of MoS2 but also maintained the metastable structure of 1T-MoS2 nanosheets, acting to reduce the activation energy for Zn2+ intercalation and enhance specific capacity. The obtained Mn-MoS2/MXene contains more 1T-MoS2 and provides an improved specific capacity of 191.7 mAh g-1 at 0.1 A g-1. Compared with Mn-MoS2 and pure MoS2, it also exhibits enhanced cycling stability with a capacity retention of 80.3% after 500 cycles at 1 A g-1. Besides, the conductivity of Mn-MoS2/MXene is significantly improved, which induces a lower activation energy of the zinc ions during intercalation/deintercalation.

Construction Strategy of VO2@V2C 1D/2D Heterostructure and Improvement of Zinc-Ion Diffusion Ability in VO2 (B).

VO2 (B) electrode material has relatively high capacity and good cycle stability. However, its poor rate performance limits its further development because of the strong interaction between zinc ions and the main lattice of VO2 (B). Herein, considering the design principle of rate performance improvement, we furnished a different scheme from a previous multistep method of the synthesis-modification strategy of pure VO2 (B). VO2@V2C 1D/2D heterostructure was constructed by controllable partial oxidation of V2C by a one-step hydrothermal method. The unique 1D/2D heterostructure improves diffusivity and reduces the diffusion size of zinc ions at the same time, which significantly improved the rate performance of VO2. The situation at the heterostructure interface is analyzed by Raman spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy. Combined with cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic intermittent title technology tests, the promotion mechanism for the rate performance of the derived VO2 is further explained. In addition, it is found that V2C MXene can be electrochemically activated when the voltage reaches 1.24 V. By further widening the voltage window to activate V2C, VO2@V2COx heterostructure was obtained, which realizes high capacity and maintains high rate performance in aqueous zinc-ion batteries. This work provides key insights for the design of high-rate-performance electrode materials for aqueous zinc-ion batteries.