Interlayer Engineering of Preintercalated Layered Oxides as Cathode for Emerging Multivalent Metal-ion Batteries: Zinc and Beyond

Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocatalysis, batteries, supercapacitors, solar cells, photocatalysis, and sensing platforms. Finally, the challenges and outlooks in this promising field are featured on the basis of its current development.

Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMn2O4/carbon composite as a new Zn-insertion cathode material in aqueous Zn(CF3SO3)2 electrolyte. In 3 M Zn(CF3SO3)2 solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g-1 and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g-1. The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and promote the use of cation-defective spinel compounds and trifluoromethanesulfonic electrolyte to develop high-performance rechargeable zinc batteries.