Lithium and Lithium Compounds

Kamienski, Conrad W.; McDonald, Daniel P.; Stark, Marshall W.

doi:10.1002/0471238961.1209200811011309.a01

Cited by 8 publications

(2 citation statements)

References 51 publications

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“…The thermal stability rises with decreasing concentration in the formulation for a given alkyllithium . The stability also increases with a decrease in the storage temperature (Table ) . Although the products of decomposition are clearly known, to explain the relative thermal stabilities will not be attempted because of the numerous variables and the extent to which they influence the degradation; however, the presence of alkoxide impurities, generated from adventitious oxygen, accelerates the rate of decomposition.…”

Section: Discussionmentioning

confidence: 99%

Preparation, Properties, and Safe Handling of Commercial Organolithiums: Alkyllithiums, Lithium sec-Organoamides, and Lithium Alkoxides

Rathman

Schwindeman²

2014

Org. Process Res. Dev.

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This review includes the preparation and properties of various organolithiums, which are commercially available, up to manufacturing scale. The interdependent properties, such as pyrophoricity, solubility, stability, and aggregation, are tabulated and discussed. These properties have a direct bearing on their chemical reactivity and requirements for safe handling and storage. Extensive guidance for storage, use, analysis, and disposal of these organolithium solutions is also provided.

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Section: Discussionmentioning

confidence: 99%

Preparation, Properties, and Safe Handling of Commercial Organolithiums: Alkyllithiums, Lithium sec-Organoamides, and Lithium Alkoxides

Rathman

Schwindeman²

2014

Org. Process Res. Dev.

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“…3 These batteries have potential applications in long-range electric vehicles, where gravimetric energy density, volumetric energy density and safety are key factors that define performance. 2 Due to the high chemical reactivity of metallic lithium 5 , safety is one of the primary concerns in all the above-mentioned applications of lithium batteries. 2 Due to the high chemical reactivity of metallic lithium 5 , safety is one of the primary concerns in all the above-mentioned applications of lithium batteries.…”

Section: Introductionmentioning

confidence: 99%

A density functional theory based study of the electron transfer reaction at the cathode–electrolyte interface in lithium–air batteries

Kazemiabnavi

Dutta

Banerjee

2015

Phys. Chem. Chem. Phys.

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The unique properties of ionic liquids such as a relatively wide electrochemical stability window and very low vapor pressure have made them promising candidates as electrolytes for improving the cyclic performance of lithium-air batteries. The local current density, which is an important parameter in determining the performance of lithium-air batteries, is a function of the rate constant of the electron transfer reactions at the surface of the cathode. In this study, a novel method based on Marcus theory is presented to investigate the effect of varying the length of the alkyl side chain of model imidazolium based cations and the operating temperature on the rates of electron transfer reactions at the cathode. The necessary free energies of all the species involved in the multi-step reduction of oxygen into the peroxide ion were calculated using density functional theory (DFT). Our results indicate that the magnitude of the Gibbs free energy for the reduction of oxygen into the superoxide ion and also for the reduction of superoxide into the peroxide ion increases with an increase in the static dielectric constant of the ionic liquid. This trend in turn corresponds to the decrease in the length of the alkyl side chain of the ionic liquid cation. Furthermore, the change in Gibbs free energy decreases with increase in the operating temperature. The inner-sphere reorganization energies were evaluated using Nelsen's four point method. The total reorganization energies of all reduction reactions increase with decrease in the length of the alkyl side chain and increase in the operating temperature. Finally, the rate constants of the electron transfer reaction involved in the reduction of oxygen were calculated. The logarithm of the reaction rate constants decreases with increase in the static dielectric constant and increases with increase in the operating temperature. Our results provide fundamental insight into the kinetics and thermodynamics of the electron transfer reactions at the cathode that will help in the identification of appropriate electrolytes for enhanced performance of lithium-air batteries.

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The behaviour of Nafion® 424 membrane in the electrochemical production of lithium hydroxide

Turan

Baloglu

Ünveren

et al. 2015

J of Chemical Tech & Biotech

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BACKGROUND: Nafion ® membranes have found several applications in chemical processes, one of which is 'salt splitting', where a salt is split to produce acid and/or alkali. So, the determination of the behaviour of this membrane in the electrolysis of certain salts is an important issue. The aim of this study is to investigate the performance of Nafion ® 424 membrane in a two-compartment membrane cell for the membrane electrolysis of lithium sulphate (Li 2 SO 4 ), where lithium hydroxide (LiOH) is the target product. RESULTS: Regression analysis was performed between conductivity and concentration to predict instantaneous electrolyteconcentration. The effects of catholyte concentration (4-8% LiOH), current density (4-16 A dm −2 ) and temperature (30-60 ∘ C) were investigated. 45-70% current efficiency; 6.1-14.6 kWh kg −1 LiOH power consumption and 140-900 g LiOH m −2 membrane h −1 production rate were obtained. A cost estimation revealed that 60 ∘ C, 8% LiOH and 4 A dm −2 are the optimum parameters within the studied range. CONCLUSION: Concentration can be successfully predicted for lithium sulphate and lithium hydroxide with the help of conductivity-concentration regression equations. Current efficiency is affected primarily by LiOH concentration with a direct proportion. Power consumption increases with the increase of current density and the decrease of temperature. Based on production cost estimation, optimum working parameters can be recommended.

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Lithium and Lithium Compounds

Cited by 8 publications

References 51 publications

Preparation, Properties, and Safe Handling of Commercial Organolithiums: Alkyllithiums, Lithium sec-Organoamides, and Lithium Alkoxides

Preparation, Properties, and Safe Handling of Commercial Organolithiums: Alkyllithiums, Lithium sec-Organoamides, and Lithium Alkoxides

A density functional theory based study of the electron transfer reaction at the cathode–electrolyte interface in lithium–air batteries

The behaviour of Nafion® 424 membrane in the electrochemical production of lithium hydroxide

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