LithiumOxygen Electrochemistry in Non‐Aqueous Solutions

Sharon, Daniel; Hirshberg, Daniel; Afri, Michal; Garsuch, Arnd; Frimer, Aryeh A.; Aurbach, Doron

doi:10.1002/ijch.201400135

Cited by 46 publications

(51 citation statements)

References 102 publications

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“…108,109 Both superoxide (O 2 −. ) and peroxide (O 2 2− ) are vigorous nucleophiles and strong bases particularly in the presence of the small, hard, electrophilic lithium cations.…”

Section: Electrolyte Solutions For Li-o 2 Systemsmentioning

confidence: 99%

Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions

Erickson

Markevich

Salitra

et al. 2015

J. Electrochem. Soc.

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Non-aqueous, rechargeable battery development is one of the most important challenges of modern electrochemistry. Li ion batteries are a commercial reality for portable electronics with intensive efforts underway to apply this technology to electro-mobility. Extensive investigations of high energy density Li-sulfur and Li-oxygen systems have also been carried-out. Efforts to promote high energy density power sources for electric vehicles have been accompanied by intensive work on the development of rechargeable sodium and magnesium batteries for load-leveling applications. The electrolyte solution is a key consideration in all batteries determining cell stability, cycle life, and safety. This review discusses the importance of solution selection for advanced, high-voltage, Li ion batteries, sodium ion batteries, as well as Li-sulfur, Li-oxygen and magnesium batteries. Li ion battery standard solutions are discussed and their further optimization is outlined. Limitations of Li metal electrodes are explained. Unique problems in the use of conventional non-aqueous solutions for Li-oxygen batteries, related to intrinsic stability, are delineated. Finally, electrolyte solutions for Mg batteries are briefly reviewed, concluding that only the relatively inert ethereal solutions are suitable for future consideration. Several systems exhibit wide electrochemical windows and reversible behavior with Mg anodes, however compatibility with high-voltage/high-capacity cathodes remains a major challenge.It is impossible to imagine modern society without electrochemical power sources. The electronic revolution relies heavily on the use of highly sophisticated portable devices -including cellular phones with amazing applications, laptops, video cameras and more. All this advancement depends on the availability of high-energy density, safe and cost-effective power sources. The challenge of discovering rechargeable power sources has increased markedly in recent years, spurred by the demand for electro-mobility to replace propulsion by fossil fuels that have traditionally powered internal combustion engines.Challenges such as electrochemical propulsion by electric vehicles (EV), and the need for large-scale storage of sustainable energy (i.e. load-levelling applications) have motivated and stimulated the development of novel rechargeable batteries and super-capacitors. Batteries deliver high energy density, but have only limited cycle life and power density; super-capacitors, on the other hand, provide high power density and very prolonged cycling. Lithium-ion batteries are the focus of intensive R&D (research and development) efforts because they promise high energy density that may be suitable for electrical propulsion. Batteries (especially those like Li ion batteries with high energy density) are exceedingly complicated devices: three active bulks and two active interfaces must function simultaneously without side reactions or detrimental reflections.Consequently, R&D of novel battery systems requires investing time and effort in...

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“…108,109 Both superoxide (O 2 −. ) and peroxide (O 2 2− ) are vigorous nucleophiles and strong bases particularly in the presence of the small, hard, electrophilic lithium cations.…”

Section: Electrolyte Solutions For Li-o 2 Systemsmentioning

confidence: 99%

Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions

Erickson

Markevich

Salitra

et al. 2015

J. Electrochem. Soc.

Self Cite

151

121

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“…40 Therefore, carried out in diglyme, we compare two salts: the standard 1 M LiTFSI and 1 M LiNO 3 . Although solvent stability remains a key issue, we demonstrate that using LiNO 3 electrolyte in polyether solutions can contribute significantly to a better performance of Li-O 2 cells.…”

Section: ■ Introductionmentioning

confidence: 99%

Catalytic Behavior of Lithium Nitrate in Li-O₂ Cells

Sharon

Hirsberg

Afri

et al. 2015

ACS Appl. Mater. Interfaces

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156

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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.

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“…© The Author The Li-air or Li-O 2 system has captured a scientific attention worldwide due to its high theoretical energy density, however many challenges in the electrochemistry of this system still remain to reach commercialization. [1][2][3][4] Those challenges have given rise to a fundamental understanding of the oxygen reduction reaction (ORR) mechanistic paths in lithium containing aprotic solvent systems. Interestingly, almost all electrochemical measurements relevant to the Li-air battery in the literature report a potential scale versus Li/Li + potential, very often without specifying the solvent, electrolyte salt and lithium concentration.…”

mentioning

confidence: 99%

Perspective—The Correct Assessment of Standard Potentials of Reference Electrodes in Non-Aqueous Solution

Mozhzhukhina

Calvo

2017

J. Electrochem. Soc.

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The challenges facing metal-air batteries have prompted fundamental studies of non-aqueous electrochemistry. However it appears that contributors in the field are not aware that the potentials of Li/Li + , Na/Na + , K/K + , and Mg/Mg 2+ electrodes depend on the nature of solvent due to the cation solvation. Therefore, it is imperative to define a clear potential scale that can be correlated in different solvents. Here we report on the strong effect of the solvent on the Li/Li + redox potential and discuss the use of the ferrocene/ferrocenium couple as internal or external standard for the measurements in non-aqueous solvents in lithium-ion and lithium-0 2 battery systems. © The Author The Li-air or Li-O 2 system has captured a scientific attention worldwide due to its high theoretical energy density, however many challenges in the electrochemistry of this system still remain to reach commercialization. [1][2][3][4] Those challenges have given rise to a fundamental understanding of the oxygen reduction reaction (ORR) mechanistic paths in lithium containing aprotic solvent systems. Interestingly, almost all electrochemical measurements relevant to the Li-air battery in the literature report a potential scale versus Li/Li + potential, very often without specifying the solvent, electrolyte salt and lithium concentration.Unlike in aqueous electrochemistry where the normal hydrogen electrode potential is the reference electrode of choice, in the lithium battery community the electrode potentials are referred to the Li/Li + system since in a lithium battery either the anode is Li metal or lithium intercalated in graphite with a redox potential very close to the metal Li/Li + electrode. Due to the strong solvation of the small lithium cation and the different electron donor capacity of different solvents, the electrode potential of Li/Li + couple strongly depends on the solvent used and it could vary by as much as half of a volt between dimethyl sulfoxide and acetonitrile. 5 Furthermore, in many reports while the potential scale is referred versus the Li/Li + , Li metal is not actually used as the reference electrode, but a different reference electrode such as Ag/Ag + is employed and then converted into the Li/Li + scale often without specifying how this was done. Current StatusBrowsing through the Li-air literature we can find that in 2009 Laoire et al. used aqueous Ag/AgCl reference electrode and repored their data versus this reference. However they also indicated that Ag/AgCl gives a potential of 2.93 V versus Li/Li + , as measured using a Li foil reference electrode in a LiPF 6 solution in organic carbonates. 6This is an example of the very rare case in the Li-air literature, where the results were reported versus actual reference employed as we can see later since almost all the literature refer to the Li/Li + scale. In 2010, the same authors used the Pt mesh as the reference electrode and reported their data versus Li/Li + . They argued that the Pt electrode was calibrated with reference to the ferrocenium ion/f...

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LithiumOxygen Electrochemistry in Non‐Aqueous Solutions

Cited by 46 publications

References 102 publications

Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions

Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions

Catalytic Behavior of Lithium Nitrate in Li-O₂ Cells

Perspective—The Correct Assessment of Standard Potentials of Reference Electrodes in Non-Aqueous Solution

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LithiumOxygen Electrochemistry in Non‐Aqueous Solutions

Cited by 46 publications

References 102 publications

Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions

Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions

Catalytic Behavior of Lithium Nitrate in Li-O2 Cells

Perspective—The Correct Assessment of Standard Potentials of Reference Electrodes in Non-Aqueous Solution

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Catalytic Behavior of Lithium Nitrate in Li-O₂ Cells