The development of rechargeable zinc ion batteries with high capacity and high cycling stability is a great challenge in aqueous solution due to hydrogen evolution and dendritic growth of zinc. In this study, we present a zinc ion secondary battery, comprising a metallic zinc anode, a bio-ionic liquid− water electrolyte, and a nanostructured prussian blue analogue (PBA) cathode. Both the Zn anode and the PBA cathode exhibit good compatibility with the bio-ionic liquid-water electrolyte, which enables the electrochemical deposition/dissolution of zinc at the zinc anode, and reversible insertion/extraction of Zn 2+ ions at the PBA cathode. The cell exhibits a well-defined discharge voltage plateau of ∼1.1 V with a specific capacity of about 120 mAh g −1 at a current of 10 mA g −1 (∼0.1 C). The Zn anode shows great reversibility, and dendrite-free Zn deposits were obtained after 100 deposition/dissolution cycles. The integration of an environmentally friendly PBA cathode, a nontoxic and low-cost Zn anode, and a biodegradable ionic liquid−water electrolyte provides new perspective to develop rechargeable zinc ion batteries for various applications in electric energy storage.

Metallic zinc is a promising anode material for rechargeable Zn-based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite-free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn-Ni alloy (η- and γ-phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well-defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni(II) . Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite-free zinc.

Ionic liquids are potential designer electrolytes for energy storage devices such as batteries and capacitors wherein by changing the cation and anion of the ionic liquid (IL) the solid/liquid interface can be tuned, thereby influencing the charge and mass transfer processes. In this paper, we show the influence of water on the electrified ionic liquid 1-ethyl-3-methyl­imidazolium trifluoro­methyl­sulfonate ([Emim]­TfO)/Au(111) interface using in situ atomic force microscopy (AFM) and spectroscopy. A clear “water in IL” to “IL in water” transition could be observed in the range of 20–30 vol % of water using vibrational spectroscopy. Above 30 vol % of water the cation–anion interaction in the ionic liquid drastically reduced, which was ascertained by both spectroscopy and interfacial studies using in situ AFM. In situ AFM results further revealed that the structure of the innermost (Stern) layer depends both on the applied electrode potential and the amount of added water. A transition from a multilayered structure to a classical double-layered structure occurred at −1.0 V on changing the water concentration from 30 to 50 vol %. Furthermore, the morphology of the electrodeposited Zn could be altered with addition of water to the electrolyte which has some potential for Zn-based batteries.

Ionic liquids (ILs) form a multilayered structure at the solid/electrolyte interface, and the addition of solutes can alter it. For this purpose, we have investigated the influence of the silver bis(trifluoromethylsulfonyl)amide (AgTFSA) concentration in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py]TFSA) on the layering using in situ atomic force microscopy. AFM investigations revealed that the Au(111)/electrolyte interface indeed depends on the concentration of the salt where a typical " IL" multilayered structure is retained only at quite low concentrations of the silver salt (e.g. ≤200 μM). However, at 200 μM AgTFSA/[Py]TFSA and above this "IL" multilayered structure is disturbed/varied. A simple double layer structure was observed at 500 μM AgTFSA in [Py]TFSA. Furthermore, the widths of the innermost layers have been found to be dependent on the concentration and on the applied electrode potentials. Our AFM results show that the concentration of solutes strongly influences the structure of the electrode/electrolyte interface and can provide new insights into the electrical double layer structure of the electrode/ionic liquid interface. We also introduce a semi-continuum theory to discuss the double layer structure.

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