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Cormac O. Laoire

Bio: Cormac O. Laoire is an academic researcher from Northeastern University. The author has contributed to research in topics: Lithium superoxide & Battery (electricity). The author has an hindex of 4, co-authored 5 publications receiving 1864 citations.

Papers
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TL;DR: In this paper, a fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in nonaqueous electrolytes has been carried out for elucidating the mechanism of the oxygen electrode processes in the rechargeable Li−air battery.
Abstract: A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in nonaqueous electrolytes has been carried out for elucidating the mechanism of the oxygen electrode processes in the rechargeable Li−air battery. Using either tetrabutylammonium hexafluorophosphate (TBAPF6) or lithium hexafluorophosphate (LiPF6) electrolyte solutions in four different solvents, namely, dimethyl sulfoxide (DMSO), acetonitrile (MeCN), dimethoxyethane (DME), and tetraethylene glycol dimethyl ether (TEGDME), possessing a range of donor numbers (DN), we have determined that the solvent and the supporting electrolyte cations in the solution act in concert to influence the nature of reduction products and their rechargeability. In solutions containing TBA+, O2 reduction is a highly reversible one-electron process involving the O2/O2− couple. On the other hand, in Li+-containing electrolytes relevant to the Li−air battery, O2 reduction proceeds in a stepwise fashion to form O2−, O22−, and O2− as products. Th...

876 citations

Journal ArticleDOI
TL;DR: In this paper, the intimate role of electrolyte, in particular the role of ion conducting salts, in determining the reversibility and kinetics of oxygen reduction in nonaqueous electrolytes designed for such applications is reported.
Abstract: Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. Abraham et al. (Abraham, K. M.; Jiang, Z. J. Electrochem. Soc. 1996, 143, 1−5) overcame this limitation by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere, forming the Li-air battery. The Li/O2 battery redox couple has a theoretical specific energy of 5200 W h/kg and represents the ultimate, environmentally friendly electrochemical power source. In this work, we report for the first time the intimate role of electrolyte, in particular the role of ion conducting salts, in determining the reversibility and kinetics of oxygen reduction in nonaqueous electrolytes designed for such applications. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reductio...

621 citations

Journal ArticleDOI
TL;DR: In this article, a rechargeable Li-air cell utilizing an electrolyte composed of a solution of LiPF 6 in tetraethylene glycol dimethyl ether, CH 3 O(CH 2 CH 2 O) 4 CH 3 (TEGDME), and an uncatalyzed porous carbon electrode, investigated to elucidate the baseline Li−air battery chemistry, is reported.
Abstract: A rechargeable Li―air cell utilizing an electrolyte composed of a solution of LiPF 6 in tetraethylene glycol dimethyl ether, CH 3 O(CH 2 CH 2 O) 4 CH 3 (TEGDME), and an uncatalyzed porous carbon electrode, investigated to elucidate the baseline Li―air battery chemistry, is reported. From the x-ray diffraction patterns of the discharged carbon electrodes, the discharge product of the cell was identified to be Li 2 O 2 during normal discharge to 1.5 V. Discharging the cell to 1.0 V or below produces Li 2 O as well. The cell can be recharged without a catalyst in the carbon cathode, albeit at low depths of discharge. The high resistance of the discharged carbon cathode is a major impediment to recharging cells displaying a high specific capacity. The cell capacity decreases with continued cycling, which was found to be due to the poor cycling efficiency of the Li anode and the high resistance of the discharge products, which slowly accumulate in the porous electrode.

420 citations

Journal ArticleDOI
TL;DR: In this article, a detailed study of the kinetics of oxidation of ferrocene to ferrocenium ion was carried out using cyclic (CV) and rotating disk electrode (RDE) voltammetry.

96 citations


Cited by
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TL;DR: The energy that can be stored in Li-air and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed.
Abstract: Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.

7,895 citations

Journal ArticleDOI
TL;DR: The Review will consider some of the current scientific issues underpinning lithium batteries and electric double-layer capacitors.
Abstract: Energy-storage technologies, including electrical double-layer capacitors and rechargeable batteries, have attracted significant attention for applications in portable electronic devices, electric vehicles, bulk electricity storage at power stations, and “load leveling” of renewable sources, such as solar energy and wind power. Transforming lithium batteries and electric double-layer capacitors requires a step change in the science underpinning these devices, including the discovery of new materials, new electrochemistry, and an increased understanding of the processes on which the devices depend. The Review will consider some of the current scientific issues underpinning lithium batteries and electric double-layer capacitors.

2,412 citations

Journal ArticleDOI
TL;DR: In this article, the authors summarized the promise and challenges facing development of practical Li−air batteries and the current understanding of its chemistry, and showed that the fundamental battery chemistry during discharge is the electrochemical oxidation of lithium metal at the anode and reduction of oxygen from air at the cathode.
Abstract: The lithium−air system captured worldwide attention in 2009 as a possible battery for electric vehicle propulsion applications. If successfully developed, this battery could provide an energy source for electric vehicles rivaling that of gasoline in terms of usable energy density. However, there are numerous scientific and technical challenges that must be overcome if this alluring promise is to turn into reality. The fundamental battery chemistry during discharge is thought to be the electrochemical oxidation of lithium metal at the anode and reduction of oxygen from air at the cathode. With aprotic electrolytes, as used in Li-ion batteries, there is some evidence that the process can be reversed by applying an external potential, i.e., that such a battery can be electrically recharged. This paper summarizes the authors’ view of the promise and challenges facing development of practical Li−air batteries and the current understanding of its chemistry. However, it must be appreciated that this perspective ...

2,308 citations

Journal ArticleDOI
TL;DR: The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes, and the design and optimization of air-electrode structure are outlined.
Abstract: Because of the remarkably high theoretical energy output, metal–air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal–air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal–air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal–air batteries (219 references).

2,211 citations