Critical aspects in the development of lithium-air batteries

Intensive research has been done on lithium-air batteries, especially in the last few years. Due to their very high theoretical specific energy, lithium-air batteries are one of the most promising candidates to power future electric vehicles. However, this new technology is in a very early stage of development, and several challenges must be overcome before there will be a commercially viable product. This review describes the most important critical aspects in the development of lithium-air batteries: the electrocatalysis of the oxygen electrode reactions, the degradation of the electrolyte and the oxygen electrode components, the structure of the oxygen electrode, and the passivation of the oxygen electrode during the discharge of the battery. Recent works in these areas are critically reviewed, and suitable research strategies to address these issues are discusse

The Role of Adsorption in the Electrocatalysis of Hydrazine on Platinum Electrodes

Hydrazine oxidation on platinum single-crystal electrodes has been studied in acidic solution containing different electrolytes. It will be shown that the hydrazinium cation is adsorbed on platinum through an anodic reaction. Moreover, in the presence of chloride, this adsorption process is favored owing to the formation of an ionic pair with adsorbed chloride. In spite of the enhanced adsorption of hydrazine species in the presence of chloride, higher overpotentials are measured in these media, which reveals that the oxidation of hydrazine not only requires adsorption, but also that the adsorption mode of the species facilitates the formation of the transition state to yield the final product.This work has been financially supported by the MINECO (Spain) and Generalitat Valenciana through projects CTQ2016-76221-P and PROMETEOII/2014/013, respectively

A new method to prevent degradation of lithium–oxygen batteries: reduction of superoxide by viologen

Lithium–oxygen battery development is hampered by degradation reactions initiated by superoxide, which is formed in the pathway of oxygen reduction to peroxide. This work demonstrates that the superoxide lifetime is drastically decreased upon addition of ethyl viologen, which catalyses the reduction of superoxide to peroxide

Solvothermal water-diethylene glycol synthesis of LiCoPO4 and effects of surface treatments on lithium battery performance

Olivine-structured LiCoPO4 is prepared via a facile solvothermal synthesis, using various ratios of water/ diethylene glycol co-solvent, followed by thermal treatment under Ar, air, 5%H2/N2 or NH3. The diethylene glycol plays an important role in tailoring the particle size of LiCoPO4. It is found that using a ratio of water/diethylene glycol of 1 : 6 (v/v), LiCoPO4 is obtained with a homogenous particle size of �150 nm. The bare LiCoPO4 prepared after heating in Ar exhibits high initial discharge capacity of 147 mA h g1 at 0.1C with capacity retention of 70% after 40 cycles. This is attributed to the enhanced electronic conductivity of LiCoPO4 due to the presence of Co2P after firing under Ar. The effects of carbon, TiN and RuO2 coating are also examined. Contrary to other studies, it is found that the solvothermally synthesised LiCoPO4 samples produced here do not require conductive coatings to achieve good performance

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.The authors thank EPSRC-EP/M009521/1 (T.L., G.K., C.P.G.), Innovate UK (T.L.), Darwin Schlumberger Fellowship (T.L.), EU Horizon 2020 GrapheneCore1-No.696656 (G.K., C.P.G.), EPSRC - EP/N024303/1, EP/L019469/1 (N.G.-A., J.T.F.), Royal Society - RG130523 (N.G.-A.), and the European Commission FP7-MC–CIG Funlab, 630162 (N.G.-A.) for research funding

Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction

The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing ‘pseudo-single-crystal’ electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe2+/3+ couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe2+ oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale

2021 roadmap on lithium sulfur batteries

Batteries that extend performance beyond the intrinsic limits of Li-ion batteries are among the most important developments required to continue the revolution promised by electrochemical devices. Of these next-generation batteries, lithium sulfur (Li–S) chemistry is among the most commercially mature, with cells offering a substantial increase in gravimetric energy density, reduced costs and improved safety prospects. However, there remain outstanding issues to advance the commercial prospects of the technology and benefit from the economies of scale felt by Li-ion cells, including improving both the rate performance and longevity of cells. To address these challenges, the Faraday Institution, the UK's independent institute for electrochemical energy storage science and technology, launched the Lithium Sulfur Technology Accelerator (LiSTAR) programme in October 2019. This Roadmap, authored by researchers and partners of the LiSTAR programme, is intended to highlight the outstanding issues that must be addressed and provide an insight into the pathways towards solving them adopted by the LiSTAR consortium. In compiling this Roadmap we hope to aid the development of the wider Li–S research community, providing a guide for academia, industry, government and funding agencies in this important and rapidly developing research space