The Effect of Water on Quinone Redox Mediators in Nonaqueous Li-O2 Batteries.

The parasitic reactions associated with reduced oxygen species and the difficulty in achieving the high theoretical capacity have been major issues plaguing development of practical nonaqueous Li-O2 batteries. We hereby address the above issues by exploring the synergistic effect of 2,5-di-tert-butyl-1,4-benzoquinone and H2O on the oxygen chemistry in a nonaqueous Li-O2 battery. Water stabilizes the quinone monoanion and dianion, shifting the reduction potentials of the quinone and monoanion to more positive values (vs Li/Li+). When water and the quinone are used together in a (largely) nonaqueous Li-O2 battery, the cell discharge operates via a two-electron oxygen reduction reaction to form Li2O2, with the battery discharge voltage, rate, and capacity all being considerably increased and fewer side reactions being detected. Li2O2 crystals can grow up to 30 µm, more than an order of magnitude larger than cases with the quinone alone or without any additives, suggesting that water is essential to promoting a solution dominated process with the quinone on discharging. The catalytic reduction of O2 by the quinone monoanion is predominantly responsible for the attractive features mentioned above. Water stabilizes the quinone monoanion via hydrogen-bond formation and by coordination of the Li+ ions, and it also helps increase the solvation, concentration, lifetime, and diffusion length of reduced oxygen species that dictate the discharge voltage, rate, and capacity of the battery. When a redox mediator is also used to aid the charging process, a high-power, high energy density, rechargeable Li-O2 battery is obtained.

Understanding LiOH Chemistry in a Ruthenium-Catalyzed Li-O2 Battery.

Non-aqueous Li-O2 batteries are promising for next-generation energy storage. New battery chemistries based on LiOH, rather than Li2 O2 , have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru-catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e- oxygen reduction reaction, the H in LiOH coming solely from added H2 O and the O from both O2 and H2 O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2 O2 , LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long-lived battery. An optimized metal-catalyst-electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.

A non-academic perspective on the future of lithium-based batteries.

In the field of lithium-based batteries, there is often a substantial divide between academic research and industrial market needs. This is in part driven by a lack of peer-reviewed publications from industry. Here we present a non-academic view on applied research in lithium-based batteries to sharpen the focus and help bridge the gap between academic and industrial research. We focus our discussion on key metrics and challenges to be considered when developing new technologies in this industry. We also explore the need to consider various performance aspects in unison when developing a new material/technology. Moreover, we also investigate the suitability of supply chains, sustainability of materials and the impact on system-level cost as factors that need to be accounted for when working on new technologies. With these considerations in mind, we then assess the latest developments in the lithium-based battery industry, providing our views on the challenges and prospects of various technologies.

Using polyoxometalates to enhance the capacity of lithium-oxygen batteries.

The Keggin-type polyoxometalate α-SiW12O404- increases the discharge capacity and potential of lithium-oxygen batteries, by facilitating the reduction of O2 to Li2O2, as confirmed by in situ electrochemical pressure measurements and XRD. Compared to organic redox mediators, polyoxometalates have higher chemical and structural stability, which could lead to longer cycling lithium-oxygen batteries.

Improving Na-O2 batteries with redox mediators.

A new route to enhance the performance of Na-O2 cells is demonstrated. Redox mediators (such as ethyl viologen) are shown to facilitate the discharge reaction, producing an increased capacity (due to suppressed electrode passivation), higher discharge potential (due to faster kinetics) and stable cycling.

In situ phase behaviour of a high capacity LiCoPO4 electrode during constant or pulsed charge of a lithium cell.

The phase changes that occur during lithium extraction from LiCoPO4 in lithium half-cells were studied using synchrotron X-ray diffraction. The existence of two two-phase regions with an intermediate phase present was observed. Significant variations in the composition of the phases of nominal stoichiometry LiCoPO4, Li2/3CoPO4 and CoPO4 resulted in unit cell volume variations. On current pulsing, lattice parameter shifts and phase recovery were directly observed.