On the Balance of Intercalation and Conversion Reactions in Battery Cathodes

We present a thermodynamic analysis of the driving forces for intercalation and conversion reactions in battery cathodes across a range of possible working ion, transition metal, and anion chemistries. Using this body of results, we analyze the importance of polymorph selection as well as chemical composition on the ability of a host cathode to support intercalation reactions. We find that the accessibility of high energy charged polymorphs in oxides generally leads to larger intercalation voltages favoring intercalation reactions, whereas sulfides and selenides tend to favor conversion reactions. Furthermore, we observe that Cr-containing cathodes favor intercalation more strongly than those with other transition metals. Finally, we conclude that two-electron reduction of transition metals (as is possible with the intercalation of a $2+$ ion) will favor conversion reactions in the compositions we studied

Transport and Magnetic Properties of FexVse2 (x = 0 - 0.33)

We present our results of the effect of Fe intercalation on the structural, transport and magnetic properties of 1T-VSe2. Intercalation of iron, suppresses the 110K charge density wave (CDW) transition of the 1T-VSe2. For the higher concentration of iron, formation of a new kind of first order transition at 160K takes place, which go on stronger for the 33% Fe intercalation. Thermopower of the FexVSe2 compounds (x = 0 - 0.33), however do not show any anomaly around the transition. The intercalation of Fe does not trigger any magnetism in the weak paramagnetic 1T-VSe2, and Fe is the low spin state of Fe3+.Comment: 7 pages, 8 figures, 2 table

The mechanism of caesium intercalation of graphene

Properties of many layered materials, including copper- and iron-based superconductors, topological insulators, graphite and epitaxial graphene can be manipulated by inclusion of different atomic and molecular species between the layers via a process known as intercalation. For example, intercalation in graphite can lead to superconductivity and is crucial in the working cycle of modern batteries and supercapacitors. Intercalation involves complex diffusion processes along and across the layers, but the microscopic mechanisms and dynamics of these processes are not well understood. Here we report on a novel mechanism for intercalation and entrapment of alkali-atoms under epitaxial graphene. We find that the intercalation is adjusted by the van der Waals interaction, with the dynamics governed by defects anchored to graphene wrinkles. Our findings are relevant for the future design and application of graphene-based nano-structures. Similar mechanisms can also play a role for intercalation of layered materials.Comment: 8 pages, 7 figures in published form, supplementary information availabl

Intercalation events visualized in single microcrystals of graphite.

The electrochemical intercalation of layered materials, particularly graphite, is fundamental to the operation of rechargeable energy-storage devices such as the lithium-ion battery and the carbon-enhanced lead-acid battery. Intercalation is thought to proceed in discrete stages, where each stage represents a specific structure and stoichiometry of the intercalant relative to the host. However, the three-dimensional structures of the stages between unintercalated and fully intercalated are not known, and the dynamics of the transitions between stages are not understood. Using optical and scanning transmission electron microscopy, we video the intercalation of single microcrystals of graphite in concentrated sulfuric acid. Here we find that intercalation charge transfer proceeds through highly variable current pulses that, although directly associated with structural changes, do not match the expectations of the classical theories. Evidently random nanoscopic defects dominate the dynamics of intercalation

Dynamics of graphite fiber intercalation: In situ resistivity measurements with a four point probe

The dynamics of ferric chloride intercalation of single graphite fibers were studied, in situ, using a four point dc bridge. Measurements before, during and after the intercalation showed that the intercalation occurred within minutes at 200 C. Changes in fiber resistivity after exposure to air suggested hydration of the graphite intercalation compound. Deintercalation of the ferric chloride was initiated at temperatures in excess of 400 C. cycling the intercalant into and out of the graphite fiber gave no improvements in fiber resistivity. The activation energy of the ferric chloride intercalation reaction was found to be 17 + or - 4 kcal/mol 1 consistent with the concept of a preliminary nucleation step in the intercalation reaction

Strong dopant dependence of electric transport in ion-gated MoS2

We report modifications of the temperature-dependent transport properties of $\mathrm{MoS_2}$ thin flakes via field-driven ion intercalation in an electric double layer transistor. We find that intercalation with $\mathrm{Li^+}$ ions induces the onset of an inhomogeneous superconducting state. Intercalation with $\mathrm{K^+}$ leads instead to a disorder-induced incipient metal-to-insulator transition. These findings suggest that similar ionic species can provide access to different electronic phases in the same material.Comment: 5 pages, 3 figure