Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Aprotic alkali metal-oxygen batteries require reversible formation of metal superoxide or peroxide on cycling. Severe parasitic reactions cause poor rechargeability, efficiency, and cycle life and have been shown to be caused by singlet oxygen ( 1 O 2 ) that forms at all stages of cycling. However, its formation mechanism remains unclear. We show that disproportionation of superoxide, the product or intermediate on discharge and charge, to peroxide and oxygen is responsible for 1 O 2 formation. While the overall reaction is driven by the stability of peroxide and thus favored by stronger Lewis acidic cations such as Li + , the 1 O 2 fraction is enhanced by weak Lewis acids such as organic cations. Concurrently, the metal peroxide yield drops with increasing 1 O 2 . The results explain a major parasitic pathway during cell cycling and the growing severity in K-, Na-, and Li-O 2 cells based on the growing propensity for disproportionation. High capacities and rates with peroxides are now realized to require solution processes, which form peroxide or release O 2 via disproportionation. The results therefore establish the central dilemma that disproportionation is required for high capacity but also responsible for irreversible reactions. Highly reversible cell operation requires hence finding reaction routes that avoid disproportionation. Broader contextDecarbonizing the energy system requires energy storage with large capacity but equally low economic and ecological footprint. Alkali metal-O 2 batteries are considered outstanding candidates in this respect. However, they suffer from poor cycle life as a result of cathode degradation. Formation of the highly reactive singlet oxygen has been proposed to cause this degradation, but formation mechanisms have remained unclear. Here, we show that the singlet oxygen source is the disproportionation of thermodynamically unstable superoxide intermediates to the peroxides. The revealed mechanism conclusively explains the strongly growing degree of degradation when going from K-O 2 to Na-O 2 and Li-O 2 cells. A major consequence is that highly reversible cell operation of Li-O 2 and Na-O 2 cells requires them to form and decompose the peroxides without disproportionation. Achieving this requires finding new reaction routes. The work lays the mechanistic foundation to fight singlet oxygen as the predominant source of degradation in metal-O 2 cells.

We report here electrochemical capacitors using an aqueous electrolyte based on the concept of "water-in-salt" with the aim to improve the energy density by increasing the voltage of the cell. A "water-in-salt" consists of a highly concentrated aqueous LiTFSI solution in which both volume and mass of LiTFSI are greater than those of water. With activated carbon supercapacitor electrodes (PICA) and 31 m "water-in-salt" electrolytes (m stands for molality), we were able to reach a cell voltage of 2.4 V whereas it is difficult to exceed 1.6 V in conventional aqueous devices because of water splitting. Moreover, it was observed that the specific capacitance of the cell is improved using "water-in-salt" electrolytes. In these conditions, an energy density of 30 Wh kg −1 was obtained which is at least three times greater than for conventional aqueous devices and in the same order of magnitude than for redox enhanced capacitors. Interestingly, fair stability, over 2000 cycles, was obtained for the 7 m electrolyte. Up to 90 sec chargingdischarging rate, this latter electrolyte offers the best compromise between voltage, power and energy densities and stability. This study demonstrates the feasibility of water-in-salt as an electrolyte for supercapacitors and points out the most suited compositions for these electrolytes.