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Related Concept Videos

SN2 Reaction: Transition State02:26

SN2 Reaction: Transition State

An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
Insensitive Nuclei Enhanced by Polarization Transfer (INEPT)01:15

Insensitive Nuclei Enhanced by Polarization Transfer (INEPT)

Insensitive Nuclei Enhanced by Polarization Transfer (INEPT) is an advanced Nuclear Magnetic Resonance (NMR) technique specifically designed to detect and enhance the signals of low-abundance nuclei, such as carbon-13 and nitrogen-15, in small molecules. The fundamental principle behind INEPT is the transfer of polarization from a more abundant and highly polarizable nucleus, typically hydrogen-1, to the low-abundance nucleus of interest. This process effectively boosts the NMR signal of the...
SN1 Reaction: Mechanism02:25

SN1 Reaction: Mechanism

Kinetic studies of ionization of a tertiary halide in a protic solvent suggest that only the substrate participates in the rate-determining step (slow step). The nucleophile is involved only after the slowest step. The SN1 reaction takes place in a multiple-step mechanism. 
Firstly, the haloalkane ionizes to generate a carbocation intermediate and a halide ion. This heterolytic cleavage is highly endothermic with large activation energy. The ionization of the substrate, facilitated by a polar...
Imperfections in Crystal Structure: Stoichiometric Point Defects01:26

Imperfections in Crystal Structure: Stoichiometric Point Defects

Schottky defects arise when some lattice points in a crystal, such as those in NaCl, remain unoccupied, creating lattice vacancies without disturbing the overall electrical neutrality of the crystal. This defect is common in ionic crystals where the positive and negative ions are similar in size, as seen in sodium chloride and cesium chloride. The presence of Schottky defects enables the crystal to conduct electricity to a small extent through an ionic mechanism. Electric fields cause nearby...
Predicting Products: SN1 vs. SN202:27

Predicting Products: SN1 vs. SN2

Nucleophilic substitution reactions of alkyl halides can proceed via an SN1 or an SN2 mechanism. While in SN2 reactions, the nucleophile attacks the substrate simultaneously as the leaving group departs, in SN1 reactions, the substrate first dissociates to give the carbocation intermediate. Various factors such as the structure of the substrate, the strength of the nucleophile, and the nature of the solvent promote one mechanism over the other.
With increased substitution on the alkyl halide,...
SN2 Reaction: Mechanism02:27

SN2 Reaction: Mechanism

The kinetic studies of SN2 reactions suggest an essential feature of its mechanism: it is a single-step process without intermediates. Here, both the nucleophile and the substrate participate in the rate-determining step.
The presence of the more electronegative halogen in the substrate creates a polarized carbon-halide bond. The halide pulls the electron cloud generating an electrophilic center at the carbon atom. Thus, the carbon atom carries a partial positive charge while the halide has a...

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Phase-sensitivity of Li intercalation into Sn.

Payam Kaghazchi1

  • 1Institute for Electrochemistry, Ulm University, Albert-Einstein-Allee 47, D-89069 Ulm, Germany. payam.kaghazchi@uni-ulm.de

Journal of Physics. Condensed Matter : an Institute of Physics Journal
|August 31, 2013
PubMed
Summary

Lithium intercalation into tin (Sn) nanoparticles shows strong phase-sensitivity. Calculations reveal alpha-Sn nanoparticles are kinetically more favorable for lithium intercalation than beta-Sn nanoparticles due to lower energy barriers.

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Area of Science:

  • Materials Science
  • Computational Chemistry
  • Electrochemistry

Background:

  • Tin (Sn) is a promising anode material for lithium-ion batteries.
  • Understanding lithium-ion transport mechanisms in Sn is crucial for battery performance.
  • Different phases of tin (alpha-Sn and beta-Sn) may exhibit distinct electrochemical behaviors.

Purpose of the Study:

  • To investigate the phase-dependent energy barriers for lithium intercalation into alpha-Sn and beta-Sn.
  • To identify the rate-limiting steps for lithium intercalation in different tin phases.
  • To compare the kinetic favorability of lithium intercalation in alpha-Sn and beta-Sn nanoparticles.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed.
  • Investigation of energy barriers for lithium diffusion and surface intercalation.
  • Analysis of rate-determining steps in both bulk and surface processes.

Main Results:

  • Significant phase-sensitivity in energy barriers for lithium intercalation into Sn was observed.
  • Bulk diffusion was the rate-limiting step in alpha-Sn, while surface penetration dominated in beta-Sn.
  • Although beta-Sn has lower bulk diffusion barriers, its surface intercalation barriers are substantially higher than alpha-Sn.

Conclusions:

  • Lithium intercalation into alpha-Sn nanoparticles is kinetically more favorable than into beta-Sn nanoparticles.
  • The distinct phase-dependent intercalation mechanisms highlight the importance of controlling Sn phase for battery anode design.
  • DFT provides valuable insights into the fundamental processes governing lithium storage in tin-based anodes.