Lithium and Lithium Compounds

Kamienski, Conrad W.; McDonald, Daniel P.; Stark, Marshall W.; Papcun, John R.

doi:10.1002/0471238961.1209200811011309.a01.pub2

Cited by 19 publications

(16 citation statements)

References 52 publications

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“…Lithium salts attract considerable interest for practical applications in battery development, medicine, automotive lubricant additives, and so on . This is largely because many of the fundamental properties of lithium salts, such as their solubility, stability, and density, are often markedly different from those of their close congeners.…”

Section: Introductionmentioning

confidence: 99%

Heat Capacities of Aqueous Solutions of Lithium Sulfate, Lithium Perchlorate, and Lithium Trifluoromethanesulfonate at 298.15 K

Hnědkovský

Hefter

2016

J. Chem. Eng. Data

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Isobaric heat capacities of aqueous solutions of Li 2 SO 4 , LiClO 4 , and LiCF 3 SO 3 have been measured at 298.15 K and 0.1 MPa up to high concentrations using a Picker flow calorimeter. Apparent molar isobaric heat capacities, C p,ϕ , derived from these data were fitted within the limits of experimental precision with an extended Redlich−Rosenfeld−Meyer type of equation, which was also used to estimate the standard state (infinite dilution) quantities, C p,ϕ o , for each salt. The latter values were combined with appropriate literature data to produce a robust estimate of C p,ϕ oWhere comparison was possible, C p,ϕ (Li n X) values were closely parallel to those of the corresponding acids over the whole concentration range, even when the shapes of the curves were highly unusual. In contrast, C p,ϕ (Na n X) values always exhibited a crossover with the lithium salt data at a concentration of about 1 mol•kg −1 , which appears to reflect differences in the hydration of the two cations.

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Section: Introductionmentioning

confidence: 99%

Heat Capacities of Aqueous Solutions of Lithium Sulfate, Lithium Perchlorate, and Lithium Trifluoromethanesulfonate at 298.15 K

Hnědkovský

Hefter

2016

J. Chem. Eng. Data

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“…) are the Gibbs free energies of the neutral oxygen molecule, superoxide and peroxide ions respectively. In addition to its dependence on the Gibbs free energy, the electron transfer rate constant is also a function of the inner-and outer-sphere reorganization energies in the framework of Marcus theory, as shown in eqn (5). The total reorganization energy is given by the summation of the innersphere and outer-sphere reorganization energies, l = l in + l out , which are independent parameters.…”

Section: àmentioning

confidence: 99%

“…1,4 Additionally, Li-air batteries can be very beneficial in powering myriad consumer electronic devices as well as remote sensors. 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. 6,7 Lithium metal is highly reactive in the presence of polar protic and aprotic organic solvents, commonly used as electrolytes in lithium batteries, and can lead to electrode-electrolyte side reactions.…”

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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“…Both studied reactions serve as starting points for a multitude of further synthesis steps. Thus, a broad spectrum of chemical reactions can be covered, acting as basic building blocks for organic-chemical compounds of industrial relevance [59][60][61][62][63][64][65].…”

Section: Introductionmentioning

confidence: 99%

Simultaneous self-optimisation of yield and purity through successive combination of inline FT-IR spectroscopy and online mass spectrometry in flow reactions

et al. 2021

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Self-optimisation constitutes a very helpful tool for chemical process development, both in lab and in industrial applications. However, research on the application of model-free autonomous optimisation strategies (based on experimental investigation) for complex reactions of high industrial significance, which involve considerable intermediate and by-product formation, is still in an early stage. This article describes the development of an enhanced autonomous microfluidic reactor platform for organolithium and epoxide reactions that incorporates a successive combination of inline FT-IR spectrometer and online mass spectrometer. Experimental data is collected in real-time and used as feedback for the optimisation algorithms (modified Simplex algorithm and Design of Experiments) without time delay. An efficient approach to handle intricate optimisation problems is presented, where the inline FT-IR measurements are used to monitor the reaction’s main components, whereas the mass spectrometer’s high sensitivity permits insights into the formation of by-products. To demonstrate the platform’s flexibility, optimal reaction conditions of two organic syntheses are identified. Both pose several challenges, as complex reaction mechanisms are involved, leading to a large number of variable parameters, and a considerable amount of by-products is generated under non-ideal process conditions. Through multidimensional real-time optimisation, the platform supersedes labor- and cost-intensive work-up procedures, while diminishing waste generation, too. Thus, it renders production processes more efficient and contributes to their overall sustainability. Graphical abstract

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Lithium and Lithium Compounds

Cited by 19 publications

References 52 publications

Heat Capacities of Aqueous Solutions of Lithium Sulfate, Lithium Perchlorate, and Lithium Trifluoromethanesulfonate at 298.15 K

Heat Capacities of Aqueous Solutions of Lithium Sulfate, Lithium Perchlorate, and Lithium Trifluoromethanesulfonate at 298.15 K

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

Simultaneous self-optimisation of yield and purity through successive combination of inline FT-IR spectroscopy and online mass spectrometry in flow reactions

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