Overview on the Chemistry of Intercalation into Graphite of Binary Metallic Alloys

Lagrange, Philippe

doi:10.1007/978-1-4615-2850-0_29

Cited by 15 publications

(8 citation statements)

References 14 publications

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“…Despite a wealth of strategies, moving a large heavy metal electrochemically is difficult due to the rate limitations associated with the size of a large atom. Intercalation of heavier atoms into 2D and layered materials has long been proposed as a route to enhance physical properties such as thermal resistivity, electron-phonon scattering, energy storage, and novel catalytic behavior [1][2][3][4][5][6][7]. Past chemical strategies include co-intercalation with an alkali, alkaline metal, or ammonia such as co-intercalation of antimony with sodium into graphite or europium into TaS 2 [2,8].…”

Section: Introductionmentioning

confidence: 99%

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides

et al. 2018

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A major outstanding challenge in the field of intercalation chemistry has been the insertion of heavy metals into a 2D layered material. Heavy metal intercalation is a promising route towards access of chemically tailored materials or enhancement of novel physics. We present a new series of wet chemical strategies to intercalate atomic heavy metal and semimetal species (Bi, Cr, Ge, Mn, Mo, Ni, Os, Pb, Pd, Pt, Rh, Ru, Sb, and W) into layered chalcogenides. Bismuth selenide, Bi2Se3, and niobium diselenide, NbSe2, are used to demonstrate this chemistry. Atomic intercalation is performed in solution using decomposition of zero-valent coordination compounds at low temperatures (∼50 °C–170 °C) or reduction with tin chloride. This host of chemical routes is non-destructive, general for chalcogens, and can be used to intercalate some lighter elements as well. These intercalation reactions more than double the current number of atomic intercalants and give access to unique physical properties including heterostructures, charge density waves, and polytypic superlattice structures.

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Section: Introductionmentioning

confidence: 99%

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides

et al. 2018

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“…This category includes weakly electropositive elements H, Hg, Tl, Bi, As [9] and strongly electronegative O, S and halogens [10,11]. All these elements behave towards graphite as electron donors (reducing agents) and generally result in poly-layered intercalated sheets.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and superconducting properties of CaC₆

Eméry¹,

Hérold²,

Marêché³

et al. 2008

Science and Technology of Advanced Materials

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Among the superconducting graphite intercalation compounds, CaC 6 exhibits the highest critical temperature T c = 11.5 K. Bulk samples of CaC 6 are obtained by immersing highly oriented pyrographite pieces in a well-chosen liquid Li-Ca alloy for 10 days at 350• C. The crystal structure of CaC 6 belongs to the R3m space group. In order to study the superconducting properties of CaC 6 , magnetisation was measured as a function of temperature and direction of magnetic field applied parallel or perpendicular to the c-axis. Meissner effect was evidenced, as well as a type II superconducting behaviour and a small anisotropy. In agreement with calculations, experimental results obtained from various techniques suggest that a classical electron-phonon mechanism is responsible for the superconductivity of CaC 6 . Application of high pressure increases the T c up to 15.1 K at 8 GPa.

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“…Graphite intercalation compounds (GICs) have shown programmable physiochemical properties for applications such as electrical conductors, catalysis, hydrogen storage, and energy storage. − Among them, alkali-ion based GICs are particularly attractive as electrodes for rechargeable batteries. , GICs exhibit tunable guest–host interactions with anions, cations, and solvated cations, enabling different battery chemistries. , One of the most extensively studied GICs is lithiated graphite (LiC 6 ), a binary GIC (b-GIC) serving as the anode in commercial Li-ion batteries (LIBs) . Researchers synthesized LiC 6 from graphite via chemical means in the 1950s, but it took over three decades to synthesize it electrochemically. − The electrochemical synthesis is more intricate, governed by the solvation structure, the thermodynamic properties of electrolytes, and the graphite–electrolyte electrochemical interphase . In conventional graphite intercalation chemistry, the interphase allows cations to transport while blocking other electrolyte components such as solvent molecules .…”

Section: Introductionmentioning

confidence: 99%

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

Tao,

Xia,

Sittisomwong

et al. 2024

J. Am. Chem. Soc.

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Traditional Li-ion intercalation chemistry into graphite anodes exclusively utilizes the cointercalation-free or cointercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfactory cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in situ synthesis of t-GIC in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GIC (b-GIC) and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional cointercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles, even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10 000 cycles. Full cells coupled with a layered cathode display remarkable cycling stability upon a 15 min charging and excellent rate capability even at −40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach for achieving fast-charging and low-temperature batteries.

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Overview on the Chemistry of Intercalation into Graphite of Binary Metallic Alloys

Cited by 15 publications

References 14 publications

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides

Synthesis and superconducting properties of CaC₆

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

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Overview on the Chemistry of Intercalation into Graphite of Binary Metallic Alloys

Cited by 15 publications

References 14 publications

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides

Synthesis and superconducting properties of CaC6

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

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Product

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Synthesis and superconducting properties of CaC₆