The development of a successful Li-O2 battery depends to a large extent on the discovery of electrolyte solutions that remain chemically stable through the reduction and oxidation reactions that occur during cell operations. The influence of the electrolyte anions on the behavior of Li-O2 cells was thought to be negligible. However, it has recently been suggested that specific anions can have a dramatic effect on the chemistry of a Li-O2 cell. In the present paper, we describe how LiNO3 in polyether solvents can improve both oxygen reduction (ORR) and oxygen evolution (OER) reactions. In particular, the nitrate anion can enhance the ORR by enabling a mechanism that involves solubilized species like superoxide radicals, which allows for the formation of submicronic Li2O2 particles. Such phenomena were also observed in Li-O2 cells with high donor number solvents, such as dimethyl sulfoxide dimethylformamide (DMF) and dimethylacetamide (DMA). Nevertheless, their instability toward oxygen reduction, lithium metals, and high oxidation potentials renders them less suitable than polyether solvents. In turn, using catalysts like LiI to reduce the OER overpotential might enhance parasitic reactions. We show herein that LiNO3 can serve as an electrolyte and useful redox mediator. NO2(-) ions are formed by the reduction of nitrate ions on the anode. Their oxidation forms NO2, which readily oxidizes to Li2O2. The latter process moves the OER overpotentials down into a potential window suitable for polyether solvent-based cells. Advanced analytical tools, including in situ electrochemical quartz microbalance (EQCM) and ESR plus XPS, HR-SEM, and impedance spectroscopy, were used for the studies reported herein.

Low-energy visible light (LEVL) has been shown to stimulate cell functions. This is called "photobiostimulation" and has been used successfully over the last three decades for treating a range of conditions, including soft tissue injuries, severe wounds, chronic pain, and more. Nevertheless, the mechanism of photobiostimulative processes is still being debated. It is obvious that, in order to interact with the living cell, light has to be absorbed by intracellular chromophores. In a search for chromophores responsible for photobiostimulation, endogenous porphyrins, mitochondrial and membranal cytochromes, and flavoproteins were found to be suitable candidates. The above-mentioned chromophores are photosensitizers that generate reactive oxygen species (ROS) following irradiation. As the cellular redox state has a key role in maintaining the viability of the cell, changes in ROS may play a significant role in cell activation. In the present review, we summarize evidence demonstrating that various ROS and antioxidants are produced following LEVL illumination. We found that very little evidence for NO formation in illuminated non-vascular smooth muscle cells exists in the literature. We suggest that the change in the cellular redox state which plays a pivotal role in maintaining cellular activities leads to photobiostimulative processes.

This paper is dedicated to studies of the electrochemical behavior, the structural and thermal features of the Ni-rich LiNi 0.5 Co 0.2 Mn 0.3 O 2 undoped and Al-doped (∼0.01 at.%) materials for positive electrodes of lithium batteries. We have found that structural characteristics of these materials are quite similar from the crystallographic point of view. It was demonstrated that Al substitution in the doped LiNi 0.5 Co 0.2 Mn 0.3 O 2 is preferred at Ni sites over Co sites, and the thermodynamic preference for Al 3+ substitutions follows the order: Ni>Co>Mn. The lower capacity fading of the Al-doped electrodes upon cycling and aging of the cells in a charged state (4.3 V) at 60 • C, as well as more stable mean voltage behavior, are likely due to the chemical and structural modifications of the electrode/solution interface. The Al-doped LiNi 0.5 Co 0.2 Mn 0.3 O 2 electrodes demonstrate also lower resistances of the surface film and charge-transfer as well as lower activation energies for the discharge process. From XPS studies we conclude that the modified stable and less resistive interface on the Al-doped particles comprises the Li + -ion conducting nano-sized centers like LiAlO 2 , AlF 3 , etc., which promote, to some extent, the Li + ionic transport to the bulk. A partial layered-to-spinel transformation was established upon cycling of LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathodes.One of the major challenges in lithium batteries technology is, undoubtedly, the further improvement of battery components -electrodes, solutions, and separators. 1-7 Among several modern strategies to improve electrochemical performance and structural characteristics of materials for positive electrodes, doping has attracted the attention of scientists over the years. This is due to the effectiveness of dopants in stabilizing the structure of materials (even in minute amounts) and thus to increase the electrochemical cycling activity and to diminish the heat evolution of the electrodes in a charged state. A variety of dopant ions, like Co 2+ , Al 3+ , Ti 4+ , Zr 4+ , Zn 2+ , Fe 3+ , Cu 2+ , and Cr 3+ , has been used to improve the stability, morphology and microstructure of cathode materials, to enhance the electrode cycleability and rate capability, and to reduce capacity fading upon cycling. 8-13 For instance, doping of LiNi 0.5 Mn 0.5 O 2 with Co, Al, Ti resulted in decrease of the irreversible capacity loss and in almost no capacity fading of the doped electrodes. 14,15 In a systematic study of the Al-doped Ni-rich electrodes (LiNi 0.8 Co 0.15 Al 0.05 O 2 ), which are promising materials for use in batteries for electromotive applications, the authors have shown high cycling stability of these electrodes upon accelerated testing. 16 Several other doping metals, such as silver, magnesium, cobalt, gallium, lanthanum, bismuth, 17-19 as well as non-metallic ions (boron, fluorine), 20,21 were also explored in an attempt to increase the electrochemical cycling behavior of cathodes (both of layered and spinel structures) and to reduce their in...

Low energy visible light (LEVL) irradiation has beenshown to exert some beneficial effects on various cell cultures. For example, it increases the fertilizing capability of sperm cells, promotes cell proliferation, induces sprouting of neurons, and more. To learn about the mechanism of photobiostimulation, we studied the relationship between increased intracellular calcium ( Life on earth is entirely dependent upon the interaction of sunlight with cells especially in plant photosynthesis (1). Sunlight also has medical benefits, which have been exploited for over thousands of years in ancient Egypt, India, and China in treating skin diseases, psoriasis, vitiligo, and even cancer (2). Recent observations show that even low energy visible light (LEVL) 1 can serve as a medical tool. For example, LEVL increases the rate of wound healing (3), enhances the fertilizing capability of sperm cells (4), and increases the rate of healing bone defects (5). In vitro studies have found that LEVL increases proliferation of cells as fibroblasts (6), keratinocytes (7), and lymphocytes (8) and induces the respiratory burst in neutrophils (9). The mechanism of photobiostimulation by LEVL is still unclear. It has been suggested that reactive oxygen species (ROS), which can be produced by photosensitization of endogenous cell chromophores such as cytochromes (10) [Ca 2ϩ ] i followed by myosin phosphorylation and cell contractions (26). Growth factors and hormones were shown to stimulate ROS production, which were dependent on [Ca 2ϩ ] i rise (27). The relationship between ROS and [Ca 2ϩ ] i has been suggested to involve the redox-sensitive transcription factor N␤, which was found to change [Ca 2ϩ ] i homeostasis in response to changes in the redox state of thiol groups (28). The kinetics that characterize the [Ca 2ϩ ] i elevation have been shown to be an important parameter determining the kind of signal that will be evoked. Livingston et al. (29) showed that high concentrations of oxidants (Ͼ50 M) caused a sustained increase in [Ca 2ϩ ] i , whereas a transient increase in [Ca 2ϩ ] i was observed following administration of a low concentration of oxidants. More than a 4-fold increase in the [Ca 2ϩ ] i level was obtained in photodynamic treatment of mouse myeloma cells that had been enriched with exogenous photosensitizers before illumination, whereas only a slight increase in [Ca 2ϩ ] i was observed in irradiated cells without exogenous photosensitizers (30).Only a few works have dealt with calcium/ROS changes following LEVL irradiation. In this study, we have investigated * The costs of publication of this article were defrayed in part by the payment of page charges. This article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. Section 1734 solely to indicate this fact.§ The article describes research performed by Ronit Lavi as partial fulfillment of the requirements for her Ph.D. degree at Bar-Ilan University. To whom correspondence should be addressed. Tel.: 972-3-5317797; Fax: 972-3-...

We report on a rigorous comparative study of nano-and microparticles of LiMn 1.5 Ni 0.5 O 4 spinel as cathode materials for Li-ion batteries. The stability of these materials in LiPF 6 /alkyl carbonate solutions in temperatures up to 70°C was explored. Capacity, cycling, rate capabilities, and impedance behavior were also studied. The methods included X-ray diffraction, Raman, X-ray photelectron, Fourier transform infrared, and electron paramagnetic resonance spectroscopies, and electron microscopy, in conjunction with standard electrochemical techniques: voltammetry, chronopotentiometry, and impedance spectroscopy. These materials show an impressive stability in solutions at elevated temperature. The use of nanomaterials was advantageous for obtaining a better rate capability of LiMn 1.5 Ni 0.5 O 4 electrodes. LiMn 1.5 Ni 0.5 O 4 particles develop a unique surface chemistry in solutions that passivates and protects them from detrimental interactions with solution species at elevated temperatures.