Preparation, Characterization, and Structure Trends for Graphite Intercalation Compounds Containing Pyrrolidinium Cations

Zhang, Hanyang; Wu, Yuanyuan; Sirisaksoontorn, Weekit; Remcho, Vincent T.; Lerner, Michael

doi:10.1021/acs.chemmater.5b04828

Cited by 21 publications

(18 citation statements)

References 44 publications

(82 reference statements)

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“…This was demonstrated by the early work of Besenhard et al on the alkali metals and the tetra alkyl-ammonium cations intercalation into graphite in DMSO [18,19] , and in DME [19] upon the carbon cathodic reduction to form a so formed ternary GICs of general composition Cn -Lix(solv)y. Similarly, it was reported in early 1980 that in solvent stable to reduction such as DMSO and DME, solvated sodium is readily intercalated into graphite and forms a stage-1 ternary GICs [11,13,18,[20][21][22] .…”

Section: Introductionmentioning

confidence: 72%

Free Energy Landscape of Sodium Solvation into Graphite

Kachmar

Goddard

2018

J. Phys. Chem. C

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Na is known to deliver very low energy capacity for sodium intercalation compared to Lithium. In this study, we use quantum mechanics based metadynamics simulations to obtain the free energy landscape for sodium ion intercalation from Dimethyl sulfoxide (DMSO) solvent into graphite. We find that the lowest free energy minima from the metadynamics are associated with sodium solvated by 3 or 4 DMSO. The free energy minima of these states are activated by a free energy of solvation computed to be 0.17 eV (DG(Na + @(DMSO)4 -DG(Na + @(DMSO)3 ~ 6.6 kBT), which in turn are the most thermodynamically stable. We observe weak interactions of sodium with graphite sheets during the unbiased and biased molecular dynamics simulations. Our simulations results suggest that solvent plays an important role in stabilizing the sodium intercalation into graphite through shielding of the sodium, and also from the interaction of the solvent with the graphite sheets. This suggests that the poor performance of Na is because the nonbonding and maybe partial covalent bonding of Na + to the DMSO is too strong compared to insertion into the graphite. This suggests that we consider solvents containing oxygen groups that might interact with Na more compatible with the bonding of Na in the GIC, but with negative charges (i.e., charge carrier nature) attach to these groups. In order to facilitate this intercalation, we propose solvents with negatively charged groups and aromatic cores (e.g., cyclic ethers) that could allow a greater rate of anion exchange to increase Na + mobility.

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Section: Introductionmentioning

confidence: 72%

Free Energy Landscape of Sodium Solvation into Graphite

Kachmar

Goddard

2018

J. Phys. Chem. C

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“…The configuration and orientation of different TAA ions depend on their dimension and symmetry. [ 95,96 ] The ion exchange method has largely expanded the available choice of intercalants for synthesizing intercalated compounds. In particular, for those ions that are not stable under the intercalation environment or the required intercalation electrochemical potential, a two‐step intercalation approach involving post‐intercalation ion exchange may be an alternate route.…”

Section: Intercalation Methods For 2d Layered Materialsmentioning

confidence: 99%

Layered Intercalation Materials

et al. 2021

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2D layered materials typically feature strong in‐plane covalent chemical bonding within each atomic layer and weak out‐of‐plane van der Waals (vdW) interactions between adjacent layers. The non‐bonding nature between neighboring layers naturally results in a vdW gap, in which various foreign species may be inserted without breaking the in‐plane covalent bonds. By tailoring the composition, size, structure, and electronic properties of the intercalated guest species and the hosting layered materials, an expansive family of layered intercalation materials may be produced with highly variable compositional and structural features as well as widely tunable physical/chemical properties, invoking unprecedented opportunities in fundamental studies of property modulation and potential applications in diverse technologies, including electronics, optics, superconductors, thermoelectrics, catalysis, and energy storage. Here, the principles and protocols for various intercalation methods, including wet chemical intercalation, gas‐phase intercalation, electrochemical intercalation, and ion‐exchange intercalation, are comprehensively reviewed and how the intercalated species alter the crystal structure and the interlayer coupling of the host 2D layered materials, introducing unusual physical and chemical properties and enabling devices with superior performance or unique functions, is discussed. To conclude, a brief summary on future research opportunities and emerging challenges in the layered intercalation materials is given.

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“…With similar electrochemistry, other alkali‐ion batteries (NIBs, PIBs, and AIBs) have also been investigated over the past few decades. We should note that, some complicated anions (eg,

{normalP normalF}_{6}^{-}

{normalB normalF}_{4}^{-}

C {normalF}_{3} S {normalO}_{3}^{normal-}

{normalC}_{6} {normalH}_{5} C {normalO}_{2}^{normal-}

, fluorosulfonyl‐(trifluoromethanesulfonyl) imide (FTFSI − ), and other ﬂuoride ions etc) and solvents (eg, H 2 SO 4 , dimethyl sulfoxide, dimethylformamide, ethyl‐methyl sulfone, and Pyr 14 TFSI, etc) can also be inserted into/extracted out the graphite under certain electrochemical environments, which may play a significant role on the performances of batteries . The characterizations on the intercalations of those inorganic/organic pieces are not well established.…”

Section: Introductionmentioning

confidence: 99%

In‐situ structural characterizations of electrochemical intercalation of graphite compounds

2019

Carbon Energy

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Graphite carbon has been successfully used for the anode materials of secondary ion batteries due to its capability of accommodating ions between graphite layers. The intercalation dynamics intrinsically determine the performance of the batteries. In this review, we summarize recent research progresses of structural characterizations on graphite intercalation in electrochemical devices, especially on the in‐situ study on the intercalations of Li/Na/K ions, normalA normall C l 4 − and other anions, or solvents. These techniques, including X‐ray, electron microscopy, Raman, neutron scattering, nuclear magnetic resonance, and optical microscopy provide direct information of the reaction dynamics and help to understand the factors affecting the electrochemical performances of metallic ion batteries.

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Preparation, Characterization, and Structure Trends for Graphite Intercalation Compounds Containing Pyrrolidinium Cations

Cited by 21 publications

References 44 publications

Free Energy Landscape of Sodium Solvation into Graphite

Free Energy Landscape of Sodium Solvation into Graphite

Layered Intercalation Materials

In‐situ structural characterizations of electrochemical intercalation of graphite compounds

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