The calculated results of FeCl3 graphite intercalation compounds show the detailed features. The stage-1 FeCl3-graphite intercalation compounds present diversified electronic properties due to the intercalant. The first-principles calculations on VASP are utilized to analyze the essential properties, such as the geometric structures, spatial charge distributions, charge variations, band structures and density of states. The density of states displays full information for an explanation of the hybridizations with the special structures van Hove singularities on it. The van Hove singularities in graphite-related systems are very important and can provide full information for examining the intercalation effects. The orbital-decomposed density of states for C atoms shows that the π bondings are orthogonal to the sp2 bondings and the C-C bondings retain in the intralayer C atoms. The Fe atoms and Cl atoms form the Fe-Cl bondings at some unique energy range, presenting the multi-orbital hybridizations of [4s, 3dxy, 3dyz, 3dxz, 3dx2-y2, 3dz2]-[3px, 3py, 3pz]. For C-Cl and Cl-Cl bonds, the unique van Hove singularities exhibit their coupling interactions, revealing the multi-orbital hybridizations of [3px, 3py, 3pz]-[ 3px, 3py, 3pz] and [3s, 3px, 3py, 3pz]-[3s, 3px, 3py, 3pz], respectively. The Fe-Cl bondings arise from multi-orbital hybridizations of [4s, 3dxy, 3dyz, 3dxz, 3dx2-y2, 3dz2]-[ 3px, 3py, 3pz]. Due to the band structures and density of states, the multi-orbital interactions between intercalants and graphene layers dominate in the low-lying energy range. The charge transfers per atom (electrons/atom) for C, Fe, Cl are -0.02 e/atom, -0.28 e/atom and +0.46 e/atom, respectively. Thus, the C atoms in graphene layers present as positive ones after intercalation, i.e., the graphite system exhibit p-type doping features in agreement with previous study.
Graphite intercalation compounds (GICs) with the geometrical anisotropy and strong electron-phonon coupling are in full swing and have shown their great potential for applications in nanodevices. I selected representative three elements in actinide group with valence electron arrangement: Thorium (Th) ([Rn]6d27s2), Uranium (U) ([Rn]5f36d17s2), Plutonium (Pu) ([Rn]5f67s2). I calculated their phonon spectra and demonstrated the atomic-scale microstructure identification of actinide graphite intercalation compounds by angle-resolved polarized Raman spectroscopy.
Angle-resolved photoemission spectroscopy and Auger electron spectroscopy have been applied to study the intercalation process of silver underneath a monolayer of graphite (MG) on Ni(111). The room-temperature deposition of silver on top of MG/Ni(111) system leads to the islands-like growth of Ag on top of the MG. Annealing of the "as-deposited" system at temperature of 350-450 C results in the intercalation of about 1-2 ML of Ag underneath MG on Ni(111) independently of the thickness of pre-deposited Ag film (3-100 A). The intercalation of Ag is followed by a shift of the graphite-derived val…
Cooperative adsorption and diffusion trapping induced by AlF3 intercalation in graphite
Instituto de Física del Litoral (IFIS-Litoral, CONICET–UNL)（里奥托尔物理研究所）；Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (CNEA)（巴里洛切原子中心，国家原子能委员会）；Departamento de Física, Facultad de Ingeniería Química, Universidad Nacional del Litoral（国立里奥托尔大学化工学院物理系）；Institute of Environmental Technology (IET), CEET, VSB – Technical University of Ostrava（俄斯特拉发理工大学CEET环境技术研究所）
Modeling layered intercalation compounds from first principles poses a problem, as many of their properties are determined by a subtle balance between van der Waals interactions and chemical or Madelung terms, and a good description of van der Waals interactions is often lacking. Using van der Waals density functionals we study the structures, phonons and energetics of the archetype layered intercalation compound Li-graphite. Intercalation of Li in graphite leads to stable systems with calculated intercalation energies of $-0.2$ to $-0.3$~eV/Li atom, (referred to bulk graphite and Li metal). T…
We report on the origin of the surface structural disordering in graphite anodes induced by lithium intercalation and deintercalation processes. Average Raman spectra of graphitic anodes reveal that cycling at potentials that correspond to low lithium concentrations in LixC (0 \leq x < 0.16) is responsible for most of the structural damage observed at the graphite surface. The extent of surface structural disorder in graphite is significantly reduced for the anodes that were cycled at potentials where stage-1 and stage-2 compounds (x > 0.33) are present. Electrochemical impedance spectra show …
Motivated by the recent discovery of superconductivity in Ca- and Yb-intercalated graphite (CaC$_{6}$ and YbC$_{6}$) and from the ongoing debate on the nature and role of the interlayer state in this class of compounds, in this work we critically study the electron-phonon properties of a simple model based on primitive graphite. We show that this model captures an essential feature of the electron-phonon properties of the Graphite Intercalation Compounds (GICs), namely, the existence of a strong dormant electron-phonon interaction between interlayer and $π^{\ast}$ electrons, for which we provi…
The essential properties of graphite-based 3D systems are thoroughly investigated by the first-principles method. Such materials cover a simple hexagonal graphite, a Bernal graphite, and the stage-1 to stage-4 Li/Li$^+$ graphite intercalation compounds. The delicate calculations and the detailed analyses are done for their optimal stacking configurations, bong lengths, interlayer distances, free electron $\&$ hole densities, Fermi levels, transferred charges in chemical bondings, atom- or ion-dominated energy bands, spatial charge distributions and the significant variations after intercalatio…
Potassium intercalation in graphite is investigated by first-principles theory. The bonding in the potassium-graphite compound is reasonably well accounted for by traditional semilocal density functional theory (DFT) calculations. However, to investigate the intercalate formation energy from pure potassium atoms and graphite requires use of a description of the graphite interlayer binding and thus a consistent account of the nonlocal dispersive interactions. This is included seamlessly with ordinary DFT by a van der Waals density functional (vdW-DF) approach [Phys. Rev. Lett. 92, 246401 (2004)…
We present detailed multi frequency resonant Raman measurements of potassium graphite intercalation compounds (GICs). From a well controlled and consecutive in-situ intercalation and high temperature de-intercalation approach the response of each stage up to stage VI is identified. The positions of the G and 2D lines as a function of staging depend on the charge transfer from K to the graphite layers and on the lattice expansion. Ab-initio calculations of the density and the electronic band-structure demonstrate that most (but not all) of the transferred charge remains on the graphene sheets a…
We use first-principles calculation within the density functional theory (DFT) to explore the electronic properties on stage-1 Li- and Li+-graphite-intercalation compounds (GIC) for different concentrations, LiCx/Li+Cx with x= 6,12,18,24,32 and 36. The essential properties, e.g. geometric structures, band structures and spatial charge distributions are determined by the hybridization of orbitals, the main focus of our works. The band structures/density of states/spatial charge distribution display that the Li-GIC possesses blue shift of fermi energy and just like metals, but the Li+-GIC still …
Graphite intercalation compounds (GICs) have a variety of functions due to their rich material variations, and thus,innovative methods for their synthesis are desired for practical applications. We have discovered that Na has a catalytic property that dramatically accelerates the formation of GICs. We demonstrate that LiC6n (n = 1, 2), KC8, KC12n (n = 2, 3, 4), and NaCx are synthesized simply by mixing alkali metals and graphite powder with Na at room temperature (~25 °C), and AEC6 (AE = Ca, Sr, Ba) are synthesized by heating Na-added reagents at 250 °C only for a few hours. The NaCx, formed b…
Electrons in isolated graphene layers are a two-dimensional gas of massless Dirac Fermions. In realistic devices, however, the electronic properties are modified by elastic deformations, interlayer coupling and substrate interaction. Here we unravel the electronic structure of doped graphene, revisiting the stage one graphite intercalation compound KC$_8$ using angle--resolved photoemission spectroscopy and ab--initio calculations. The full experimental dispersion is in excellent agreement to calculations of doped graphene once electron correlations are included on the $GW$ level. This highlig…
Up to now, many guest atoms/molecules/ions have been successfully synthesized into graphite to form the various compounds. For example, alkali-atom graphite intercalation compounds are verified to reveal the stage-n structures, including LiC6n and LiM8n [M=K. Rb and Cs; n=1, 2, 3; 4]. On the other side, AlCl4-ion/molecule ones are examined to show stage-4 and stage-3 cases at room and lower temperatures, respectively. Stage-1 and stage-2 configurations, with the higher intercalant concentrations, are unable to synthesize in experimental laboratories. This might arise from the fact that it is q…
The high pressure phase diagram of CsC8 graphite intercalated compound has been investigated at ambient temperature up to 32 GPa. Combining X-ray and neutron diffraction, Raman and X- ray absorption spectroscopies, we report for the first time that CsC8, when pressurized, undergoes phase transitions around 2.0, 4.8 and 8 GPa. Possible candidate lattice structures and the transition mechanism involved are proposed. We show that the observed transitions involve the structural re- arrangement in the Cs sub-network while the distance between the graphitic layers is continuously reduced at least up…
Study of In-plane and Interlayer Interactions During Aluminum Fluoride Intercalation in Graphite: Implications for the Development of Rechargeable Batteries
A method to produce suspensions of graphene sheets by combining solution-based bromine intercalation and mild sonochemical exfoliation is presented. Ultrasonic treatment of graphite in water leads to the formation of suspensions of graphite flakes. The delamination is dramatically improved by intercalation of bromine into the graphite before sonication. The bromine intercalation was verified by Raman spectroscopy as well as by x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations show an almost ten times lower interlayer binding energy after introducing Br2 i…
We present a detailed in-situ Raman analysis of stage-1 KC8, CaC6, and LiC6 graphite intercalation compounds (GIC) to unravel their intrinsic finger print. Four main components were found between 1200 cm-1 and 1700 cm-1, and each of them were assigned to a corresponding vibrational mode. From a detailed line shape analysis of the intrinsic Fano-lines of the G- and D-line response we precisely determine the position (ωph), line width (Γph) and asymmetry (q) from each component. The comparison to the theoretical calculated line width and position of each component allow us to extract the electro…
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, which in turn are the most thermodynamically stable. We observe weak interactions of sodium …
Motivated by recent experimental work, we use first-principles density functional theory methods to conduct an extensive search for low enthalpy structures of C$_6$Ca under pressure. As well as a range of buckled structures, which are energetically competitive over an intermediate range of pressures, we show that the high pressure system ($\gtrsim 18$ GPa) is unstable towards the formation of a novel class of layered structures, with the most stable compound involving carbon sheets containing five- and eight-membered rings. As well as discussing the energetics of the different classes of low e…
The diversified essential properties of the stage-n graphite alkali-intercalation compounds are thoroughly explored by the first-principles calculations. According to their main features, the lithium and non-lithium materials might be quite different from each other in stacking configurations, the intercalated alkali-atom concentrations, the free conduction electron densities, and the atom-dominated & (carbon, alkali)-co-dominated energy bands. The close relations between the alkali-doped metallic behaviors and the geometric symmetries will be clarified through the interlayer atomic interactio…
The cointercalation of sodium with the solvent organic molecule into graphite can resolve difficulty of forming the stage-I Na-graphite intercalation compound, which is a predominant anode of Na-ion battery. To clarify the mechanism of such cointercalation, we investigate the atomistic structure, energetics, electrochemical properties, ion and electron conductance, and charge transferring upon de/intercalation of the solvated Na-diglyme ion into graphite with {\it ab initio} calculations. It is found that the Na(digl)$_2$C$_n$ compound has the negatively lowest intercalation energy at $n\appro…
We use anhydrous ferric chloride (FeCl3) to intercalate graphite flakes consisting of 2 to 4 graphene layers and to dope graphene monolayers. The intercalant, staging, stability and doping of the resulting intercalation compounds (ICs) are characterized by Raman scattering. The G peak of monolayer graphene heavily-doped by FeCl3 upshifts to~1627cm-1. 2-4 layer ICs have similar upshifts, and a Lorentzian lineshape for the 2D band, indicating that each layer behaves as a decoupled heavily doped monolayer. By performing Raman measurement at different excitation energies we show that, for a given …
The market quest for fast-charging, safe, long-lasting and performant batteries drives the exploration of new energy storage materials, but also promotes fundamental investigations of materials already widely used. Presently, revamped interest in anode materials is observed -- primarily graphite electrodes for lithium-ion batteries. Here, we focus on the upper limit of lithium intercalation in the morphologically quasi-ideal highly oriented pyrolytic graphite (HOPG), with a LiC$_6$ stoichiometry corresponding to 100\% state of charge (SOC). We prepared a sample by immersion in liquid lithium a…
GICs doped with elements containing d and f orbitals have been studied rarely. We control the distribution and density of intercalated actinide metals (Th, U and Pu), and consider the effect of changing the distance of two adjacent carbon layers on the electronic structure so as to infer the physical properties of such materials under high pressure or high temperature - which is of great significance in fundamental research. According to band schemas, those GICs are all metallic. The projected density of states (PDOS) indicates that the metal atoms first undergo hybridization of its s, p, d, a…
Graphite is the most widely used and among the most widely-studied anode materials for lithium-ion batteries. With increasing demands on lithium batteries to operate at lower temperatures and higher currents, it is crucial to understand lithium intercalation in graphite due to issues associated with lithium plating. Lithium intercalation into graphite has been extensively studied theoretically using density functional theory (DFT) calculations, complemented by experimental studies through X-ray diffraction, spectroscopy, optical imaging and other techniques. In this work, we present a first pr…
A general method was developed to intercalate metals under layered materials through a controlled density of sputtered defects. The method has been already applied to study a range of metals intercalated under graphite and different types of morphologies were realized. In the current work, we extend the method to the study of intercalation under MoS2 noting that work on this system is rather limited. We use Cu as the prototype metal for comparison with Cu intercalation under graphite. Although the growth conditions needed for intercalation under graphite and MoS2 are similar, the type of inter…
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 rep…
We offer a brief overview of the solvent-based graphene production and summarize the current knowledge on the formation mechanism of graphite oxide that proceeds via graphite intercalation compounds. In addition, the results of our in situ X-ray diffraction investigation into this process are presented, discussed and contrasted to the findings by other authors, who employed the same oxidation protocol but examined the samples by ex situ X-ray diffraction. Our results suggest that, contrary to the numerous reports by other authors, no strong crystalline order, unique to graphite intercalation c…
In this letter, we report the discovery of superconductivity in Li3Ca2C6. Several graphite intercalation compounds (GICs) with electron donors, are well known as superconductors. It is probably not astonishing, since it is generally admitted that low dimensionality promotes high superconducting transition temperatures. Superconductivity is lacking in pristine graphite, but after charging the graphene planes by intercalation, its electronic properties change considerably and superconducting behaviour can appear. Li3Ca2C6 is a ternary GIC, for which the intercalated sheets are very thick and pol…
During the reversible insertion of ions, lattices in intercalation materials undergo structural transformations. These lattice transformations generate misfit strains and volume changes that, in turn, contribute to the structural decay of intercalation materials and limit their reversible cycling. In this paper, we draw on insights from shape-memory alloys, another class of phase transformation materials, that also undergo large lattice transformations but do so with negligible macroscopic volume changes and internal stresses. We develop a theoretical framework to predict structural transforma…
Graphene has attracted great attentions since its first discovery in 2004. Various approaches have been proposed to control its physical and electronic properties. Here, we report that graphene based intercalation compounds is an efficient method to modify the electronic properties of few layer graphene (FLG). FeCl3 intercalated FLG were successfully prepared by two-zone vapor transport method. This is the first report on full intercalation for graphene samples. The features of the Raman G peak of such few-layer graphene intercalation compounds (FLGIC) are in good agreement with their full int…
Existence of van der Waals gaps renders two-dimensional (2D) materials ideal passages of lithium for being used as anode materials. However, the requirement of good conductivity significantly limits the choice of 2D candidates. So far only graphite is satisfying due to its relatively high conductivity. Recently, a new polymorph of layered germanium selenide (Gamma-GeSe) was proven to be semimetal in its bulk phase with a higher conductivity than graphite while its monolayer behaves semiconducting. In this work, by using first-principles calculations, we examined the possibility of using this n…
Intercalation materials are promising candidates for reversible energy storage and are, for example, used as lithium-battery electrodes, hydrogen-storage compounds, and electrochromic materials. An important issue preventing the more widespread use of these materials is that they undergo structural transformations (of up to ~10% lattice strains) during intercalation, which expand the material, nucleate microcracks, and, ultimately, lead to material failure. Besides the structural transformation of lattices, the crystallographic texture of the intercalation material plays a key role in governin…
Interlayer space in graphite is impermeable to ions and molecules, including protons. Its controlled expansion would find several applications in desalination, gas purification, high-density batteries, etc. In the past, metal intercalation has been used to modify graphitic interlayer spaces; however, resultant intercalation compounds are unstable in water. Here, we successfully expanded graphite interlayer spaces by intercalating aqueous KCl ions electrochemically. The water conductivity shows several orders of enhancement when compared to unintercalated graphite. Water evaporation experiments…
Various bandstructure engineering methods have been studied to improve the performance of graphitic transparent conductors; however none demonstrated an increase of optical transmittance in the visible range. Here we measure in situ optical transmittance spectra and electrical transport properties of ultrathin-graphite (3-60 graphene layers) simultaneously via electrochemical lithiation/delithiation. Upon intercalation we observe an increase of both optical transmittance (up to twofold) and electrical conductivity (up to two orders of magnitude), strikingly different from other materials. Tran…
Graphite has been reported to have anion as well as cation intercalation capacities as both cathode and anode host materials for the dual ion battery. In this work, we study the intercalation of bis(trifluoromethanesulfonyl) imide (TFSI) anion from ionic liquid electrolyte into graphite with first-principles calculations. We build models for TFSI-C$_n$ compounds with systematically increasing unit cell sizes of graphene sheet and investigate their stabilities by calculating the formation energy, resulting in the linear decrease and arriving at the limit of stability. With identified unit cell …
We present a study of charge transfer in Na-intercalated FeOCl and polyaniline-intercalated FeOCl using high-resolution x-ray absorption spectroscopy and resonant x-ray emission spectroscopy at the Fe-K edge. By comparing the experimental data with ab-initio simulations, we are able to unambiguously distinguish the spectral changes which appear due to intercalation into those of electronic origin and those of structural origin. For both systems, we find that about 25% of the Fe sites are reduced to Fe2+ via charge transfer between FeOCl and the intercalate. This is about twice as large as the …
In this letter, we study the stability of the domain model for lithium intercalated graphite in stages III and II by means of Density Functional Theory and Kinetic Lattice Monte Carlo simulations. We find that the domain model is either thermodynamically or kinetically stable when compared to the standard model in stages III and II. The existence of domains in the intercalation sequence is well supported by recent high resolution transmission electron microscope observations in lithiated graphite. Moreover, we predict that such domain staging sequences leads to a wide range of diffusivity as r…
We present a linear stability analysis to demonstrate that a flat coherent phase boundary formed by the (de)intercalation of solutes into a compound is unstable against perturbations with wavelengths larger than a critical wavelength. This critical wavelength is controlled by the competition between the interface energy and the elastic strain energy caused by the misfit between the solute-rich and solute-poor phases. It increases with the distance between the phase boundary and free surface of the compound, and so the instability is most pronounced when the boundary is close to the surface at …
New intercalation compounds Cr$_x$ZrTe$_2$ were synthesized in the Cr concentration range of x=0-0.3. A thorough study of the crystal and electronic structure has been performed. It was found that there is competition in the distribution of the Cr atoms over the octa- and tetrahedral sites in the van der Waals gap, depending on the Cr content. The ordering of the Cr atoms was found at x = 0.25; at the same time, the lattice symmetry decreases from trigonal P-3m1 to monoclinic F2/m. This ordering stabilizes the octahedral coordination of the Cr atoms by Te atoms. The analysis of the experimenta…
Highly oriented pyrolitic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on HOPG surface at room temperature, they arrange in two configurations: silicene nanosheets and three dimensional clusters. In this work we demonstrate, by using scanning tunneling microscopy (STM) and Raman spectroscopy, that a third configuration stabilizes in the form of Si 2D nanosheets intercalated below the first top layer of carbon atoms. The Raman spectra reveal a structu…
A series of molybdenum disulfide intercalation compounds was prepared to study the effect of varying loadings of the samples with intercalated molecules. The molecules, (5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene) macrocycles, occupy the gallery spaces between the MoS2 layers in a single layer. The samples were characterized by thermogravimetry, wide angle X-ray scattering, scanning electron microscopy and transmission electron microscopy (TEM). TEM images reveal the layer stacking as the filling of the gallery spaces with macrocycles increases gradually up to one mo…
The intercalation of alkali ions into layered materials has played an essential role in battery technology since the development of the first lithium-ion electrodes. Coulomb repulsion between the intercalants leads to ordering of the intercalant sublattice, which hinders ionic diffusion and impacts battery performance. While conventional diffraction can identify the long-range order that can occur at discrete intercalant concentrations during the charging cycle, it cannot determine short-range order at other concentrations that also disrupt ionic mobility. In this article, we show that the use…
Lithium intercalation into graphite is the foundation for the lithium-ion battery, and the thermodynamics of the lithiation of graphitic electrodes have been heavily investigated. Intercalated lithium in bulk graphite undergoes structural ordering known as staging to minimize electrostatic repulsions within the crystal lattice. While this process is well-understood for bulk graphite, confinement effects become important at the nanoscale, which can significantly impact the electrochemistry of nanostructured electrodes. Therefore, graphene offers a model platform to study intercalation dynamics …
Gold intercalation between the buffer layer and a graphene monolayer of epitaxial graphene on SiC(0001) leads to the formation of quasi free standing small aggregates of clusters. Angle Resolved Photoemission Spectroscopy measurements reveal that these clusters preserve the linear dispersion of the graphene quasiparticles and surprisingly increase their Fermi velocity. They also strongly modify the band structure of graphene around the Van Hove singularities (VHs) by a strong extension without charge transfer. This result gives a new insight on the role of the intercalant in the renormalizatio…
We show using scanning tunneling microscopy, spectroscopy, and ab initio calculations that several intercalation structures exist for Na in epitaxial graphene on SiC(0001). Intercalation takes place at room temperature and Na electron-dopes the graphene. It intercalates in-between single-layer graphene and the carbon-rich interfacial layer. It also penetrates beneath the interfacial layer and decouples it to form a second graphene layer. This decoupling is accelerated by annealing and is verified by direct Na deposition onto the interface layer. Our observations show that intercalation in grap…
