Ionic liquid electrolytes as a platform for rechargeable metal–air batteries: a perspective

Metal-air batteries are a well-established technology that can offer high energy densities, low cost and environmental responsibility. Despite these favourable characteristics and utilisation of oxygen as the cathode reactant, these devices have been limited to primary applications, due to a number of problems that occur when the cell is recharged, including electrolyte loss and poor efficiency. Overcoming these obstacles is essential to creating a rechargeable metal-air battery that can be utilised for efficiently capturing renewable energy. Despite the first metal-air battery being created over 100 years ago, the emergence of reactive metals such as lithium has reinvigorated interest in this field. However the reactivity of some of these metals has generated a number of different philosophies regarding the electrolyte of the metal-air battery. Whilst much is already known about the anode and cathode processes in aqueous and organic electrolytes, the shortcomings of these electrolytes (i.e. volatility, instability, flammability etc.) have led some of the metal-air battery community to study room temperature ionic liquids (RTILs) as non-volatile, highly stable electrolytes that have the potential to support rechargeable metal-air battery processes. In this perspective, we discuss how some of these initial studies have demonstrated the capabilities of RTILs as metal-air battery electrolytes. We will also show that much of the long-held mechanistic knowledge of the oxygen electrode processes might not be applicable in RTIL based electrolytes, allowing for creative new solutions to the traditional irreversibility of the oxygen reduction reaction. Our understanding of key factors such as the effect of catalyst chemistry and surface structure, proton activity and interfacial reactions is still in its infancy in these novel electrolytes. In this perspective we highlight the key areas that need the attention of electrochemists and battery engineers, in order to progress the understanding of the physical and electrochemical processes in RTILs as electrolytes for the various forms of rechargeable metal-air batteries.

Electrochemical and physicochemical properties of small phosphonium cation ionic liquid electrolytes with high lithium salt content

Electrolytes of a room temperature ionic liquid (RTIL), trimethyl(isobutyl)phosphonium (P111i4) bis(fluorosulfonyl)imide (FSI) with a wide range of lithium bis(fluorosulfonyl)imide (LiFSI) salt concentrations (up to 3.8 mol kg−1 of salt in the RTIL) were characterised using a combination of techniques including viscosity, conductivity, differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), nuclear magnetic resonance (NMR) and cyclic voltammetry (CV). We show that the FSI-based electrolyte containing a high salt concentration (e.g. 1:1 salt to IL molar ratio, equivalent to 3.2 mol kg−1 of LiFSI) displays unusual transport behavior with respect to lithium ion mobility and promising electrochemical behavior, despite an increase in viscosity. These electrolytes could compete with the more traditionally studied nitrogen-based ionic liquids (ILs) in lithium battery applications.

Stable zinc cycling in novel alkoxy-ammonium based ionic liquid electrolytes

High-energy density Zinc-air batteries are currently of interest since they could play a key role in emerging large-scale energy storage applications. However, achieving good rechargeability of such metal-air batteries requires significant further research and development effort. Room Temperature Ionic liquids (RTILs) offer a number of ideal thermal and physical properties as potential electrolytes for large-scale energy storage applications and thus, can help increase the practicality of such electrochemical devices. This paper reports the synthesis and application of three novel quaternary alkoxy ammonium bis(trifluoromethylsulfonyl)amide based RTILs, with two or more ether functional groups designed to interact and solubilize zinc ions, in order to aid in the electrochemical reversibility of the metal. The anion is successfully reduced from, and re-oxidized into, the three alkoxy ammonium RTILs suggesting that they are potential candidates as electrolytes for use in zinc-air batteries. Cyclic voltammetry reveals that the presence of water reduces the activation barrier required to deposit zinc and assists stable charge/discharge cycling in an electrolyte consisting of 0.1 M Zn(NTf2)2 in the tri-alkoxy ammonium chain RTIL, [N2(20201)(20201)(20201)] [NTf2], with 2.5 wt.% H2O. Further experiments demonstrate that with such electrolyte a Zn electrode can complete at least 750 cycles at a current density of 0.1 mA/cm2 at room temperature.