Binding of Ether and Carbonyl Oxygens to Lithium Ion

Blint, Richard J.

doi:10.1149/1.2048519

Cited by 87 publications

(76 citation statements)

References 3 publications

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“…This type of isotope effect may exist in process (i). Lithium ions are selectively coordinated by EC molecules in the EC/MEC mixed solution and the solvation number of the lithium ion is four in the primary solvation sphere [16,17]. The separation factor, S dif , expected for the diffusion process of Li + (EC) 4 in the electrolyte is then estimated to be 1.0014, much smaller than the S values observed in this work.…”

Section: Lithium Isotope Effectscontrasting

confidence: 59%

“…The integrated quantity of electricity was varied from 6.1 to 54.5 C, and the chemical formula of the formed Li-GICs calculated from the integrated quantities of electricity and the amount of graphite flakes loaded on the copper foils was from Li 0.029 C to Li 0. 16 C. An example of the changes of the cathode potential and the electric current during an electrolytic course (Run LC2-3) is shown in Figure 3. The cathode potential swiftly decreased at the very beginning of the electrolysis, reached the predetermined value (0.02 V in this case) and was kept constant thereafter.…”

Section: Resultsmentioning

confidence: 99%

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Lithium Isotope Effect Accompanying Electrochemical Intercalation of Lithium into Graphite

Yanase

Hayama

2003

Zeitschrift Für Naturforschung A

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Lithium has been electrochemically intercalated from a 1:2 (v/v) mixed solution of ethylene carbonate (EC) and methylethyl carbonate (MEC) containing 1 M LiClO 4 into graphite, and the lithium isotope fractionation accompanying the intercalation was observed. The lighter isotope was preferentially fractionated into graphite. The single-stage lithium isotope separation factor ranged from 1.007 to 1.025 at 25 • C and depended little on the mole ratio of lithium to carbon of the lithium-graphite intercalation compounds (Li-GIC) formed. The separation factor inceased with the relative content of lithium. This dependence seems consistent with the existence of an equilibrium isotope effect between the solvated lithium ion in the EC/MEC electrolyte solution and the lithium in graphite, and with the formation of a solid electrolyte interfaces on graphite at the early stage of intercalation.

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Section: Lithium Isotope Effectscontrasting

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Lithium Isotope Effect Accompanying Electrochemical Intercalation of Lithium into Graphite

Yanase

Hayama

2003

Zeitschrift Für Naturforschung A

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“…A combined photoelectron spectroscopy and ab initio investigation of the complexes of HF with dimethyl ether and dimethyl sulÐde have been carried out by Carnovale et al 25 LiF complexes of ammonia and water have been investigated theoretically by few authors26h31 and Ault and Pimental32 have provided structures of and H 3 NÉ É ÉLiCl by studying the vibrations of these complexes H 3 NÉ É ÉLiBr isolated in inert matrices. Li`affinity of dimethyl ether has been reported by Abboud et al, 33 Blint,34 and also by Smith et al 35 Woodin and Beauchamp36 have studied the Li`affinity of trimethylamine and dimethyl ether. We present here an ab initio and DFT computational study of LiF/HF complexes with the above lone pair donors, and compare our results with the available experimental values.…”

Section: Introductionmentioning

confidence: 81%

Ab initio and DFT investigations of lithium/hydrogen bonded complexes of trimethylamine, dimethyl ether and dimethyl sulfide

Ammal¹,

Venuvanalingam²

1998

Faraday Trans.

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Ab initio and DFT investigations of lithium/hydrogen bonded complexes of trimethylamine, dimethyl ether and dimethyl sulÐde S. Salai Cheettu Ammal¤ and P. Venuvanalingam* Department of Chemistry, Bharathidasan University, T iruchirappalli -620 024, India 17th June 1998, Accepted 24th June 1998 Recei¿ed Ab initio and DFT computations have been carried out on LiF and HF complexes of a set of n-donors viz. trimethylamine, dimethyl ether and dimethyl sulÐde with a 6-31]]G(d,p) basis set. The e †ect of correlation has been included with MP2, MP4 and DFT calculations. NBO analyses of the wavefunctions have been performed to examine the intermolecular interaction at the orbital level. Calculations reveal that these donors form strong n ] r* complexes and computed binding energies of the complex agree very well (CH 3 ) 2 OÉ É ÉHF with the experimental binding energies from IR spectroscopy. LiF forms stronger complexes than HF, and the e †ect of correlation on the hydrogen bond energy is considerable compared to the lithium bond energy. Though charge transfer interaction contributes to the stability of both LiF and HF complexes, it plays a less dominant role in lithium bonded complexes. While amine and ether donate their lone pair, sulÐde donates n s an lone pair and this results in perpendicular intermolecular bonds in sulÐde complexes.n p

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“…EC, with high polarity and dielectric constant, is one of the most important ingredients in the electrolyte. In 1995, Blint 58 calculated the binding energy of Li + with EC and showed that it is higher than water and several other ether and carbonyl oxygen containing species. In 2000, Li and Balbuena 14 first applied QC to investigate the experimentally proposed EC reduction mechanism proposed by Aurbach et al 59 This is a significant step, as the majority of SEI reaction mechanisms in the literature were deduced from experimentally observed products, and QC can confirm these mechanisms by calculating the energies of the intermediate structures along the proposed reaction pathways.…”

Section: Ec Solvent Decomposition Mechanismmentioning

confidence: 99%

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

et al. 2018

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A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li + transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multiscale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

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Binding of Ether and Carbonyl Oxygens to Lithium Ion

Cited by 87 publications

References 3 publications

Lithium Isotope Effect Accompanying Electrochemical Intercalation of Lithium into Graphite

Lithium Isotope Effect Accompanying Electrochemical Intercalation of Lithium into Graphite

Ab initio and DFT investigations of lithium/hydrogen bonded complexes of trimethylamine, dimethyl ether and dimethyl sulfide

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

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