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 doping level, the 2D peak can be suppressed by Pauli blocking for laser energy below the doping level. Thus, multi-wavelength Raman spectroscopy allows a direct evaluation of the Fermi level, complementary to that derived by Raman measurements at excitation energies higher than the doping level. We estimate a Fermi level shift of~0.9eV. These ICs are ideal test-beds for the physical and chemical properties of heavily-doped graphenes.
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.
Enrichment of rhombohedral stacking by mechanical exfoliation of graphite
Hungarian Research Network, Centre for Energy Research（匈牙利研究网络能源研究中心）；MTA - HUN-REN EK Lendület “Momentum” Topology in Nanomaterials Research Group（MTA-HUN-REN EK Lendulet“动量”纳米材料拓扑研究组）；Óbuda University（奥比乌斯大学）；Budapest University of Technology and Economics（布达佩斯技术与经济大学）；ELTE Eötvös Loránd University（罗兰大学）
Study of In-plane and Interlayer Interactions During Aluminum Fluoride Intercalation in Graphite: Implications for the Development of Rechargeable Batteries
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）
Li intercalation in graphite: a van der Waals density-functional study
从第一原理建模层状层间化合物提出了一个问题，因为它们的许多性质是由范德华相互作用和化学或马德隆项之间的微妙平衡决定的，并且通常缺乏对范德华相互作用的良好描述。利用van der Waals密度泛函方法研究了锂-石墨原型层间化合物的结构、声子和能量学。Li在石墨中的嵌入导致稳定的系统，其具有计算的嵌入能为$-0.2$至$-0.3$ ~eV/Li原子（指块状石墨和Li金属）。完全负载的阶段1和阶段2化合物LiC $_6$和$_{1/2}$ C $_6$是稳定的，对应于插入两个石墨烯平面之间的Li原子的二维$\sqrt3\times\sqrt3$晶格。阶段$N>2$结构与具有相同浓度的稀释阶段2化合物相比是不稳定的。在升高的温度下，稀释阶段2化合物容易变得无序，但Li $_{3/16}$ C $_6$的结构相对稳定，对应于Li原子的$\sqrt7\times\sqrt7$面内堆积。第一性原理计算，以及有限温度效应的贝特-佩尔斯模型，允许观察到的电压分布的微观描述。
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…
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…
Semiconductor InSb nanosheet/hexagonal boron nitride (hBN)/graphite trilayers are fabricated, and single- and double-gate devices made from the trilayers are realized and characterized. The InSb nanosheets employed in the trilayer devices are epitaxially grown, free-standing, zincblende crystals and are in micrometer lateral sizes. The hBN and graphite flakes are obtained by exfoliation. Each trilayer is made by successively stacking an InSb nanosheet on an hBN flake and on a graphite flake using a home-made alignment stacking/transfer setup. The fabricated single- and double-gate devices are …
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…
Few layer graphene (FLG) was synthesized by $μ$-wave assisted exfoliation of expanded graphite in toluene with an overall yield from c.a. 7% to 20%. A significant difference in the absorption of $μ$-waves by the expanded graphite and toluene allowed a rapid heating of the medium. The number of FLG sheets varies from 3 to 12, while the lateral size of the sheets exceeds few $μ$ms. The obtained FLG exhibits very low resistance with average value of 1.6 k$Ω$ (500 $Ω$ minimum) which is comparable to that of high quality graphenes synthesized by CVD methods, and lower than numbers of exfoliated gra…
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 …
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…
Effect of thermal annealing on the heat transfer properties of reduced graphite oxide flakes: a nanoscale characterization via scanning thermal microscopy
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…
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…
Ab initio study of sodium cointercalation with diglyme molecule into graphite
钠与溶剂有机分子共插层石墨，可以解决形成钠离子电池主要阳极--Ⅰ级钠-石墨层间化合物的困难。为了阐明这种共插层的机理，我们用{ \it ab initio}计算方法研究了溶剂化的Na-二甘醇二甲醚离子在石墨中脱嵌的原子结构、能量学、电化学性质、离子电导和电子电导以及电荷转移.发现Na（digl）$_2$ C $_n$化合物在$n\approx$ 21处具有负最低的嵌入能，溶剂化的Na（digl）$_2$离子在层间空间扩散快，与石墨相比，它们的电子电导可以增强。计算结果表明，二甘醇二甲醚分子和Na原子向石墨烯层提供电子，导致石墨烯层与二甘醇二甲醚分子之间形成离子键。这项工作将有助于开发创新的阳极材料的碱离子电池的应用。
The van der Waals magnets CrX$_3$ (X = I, Br, and Cl) exhibit highly tunable magnetic properties and are promising candidates for developing novel two-dimensional (2D) magnetic devices such as magnetic tunnel junctions and spin tunneling transistors. Previous studies of CrCl$_3$ have mainly focused on mechanically exfoliated samples. Controlled synthesis of high quality atomically thin flakes is critical for their technological implementation but has not been achieved to date. Here, we report the growth of large CrCl$_3$ flakes with well-defined facets down to monolayer thickness (~0.6 nm) via…
Transition-metal-dichalcogenides own a variety of structures as well as electronic properties which can be modulated by structural variations, element substitutions, ion or molecule intercalations, etc. However, there is very limited knowledge on metastable phases of this family, especially the precise regulation of structural changes and accompanied evolution of electronic properties. Here, based on a new developed field-effect transistor with solid ion conductor as the gate dielectric, we report a controllable structural and electronic phase transitions in metastable MoS$_2$ thin flakes driv…
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 …
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 novel WS2-graphite dual-ion battery (DIB) is developed by combining together a conventional graphite cathode and high-capacity few-layer WS2 flakes anode. The WS2 flakes are produced by exploiting wet-jet milling (WJM) exfoliation, which allows mass production of few-layer WS2 flakes in dispersion, with an exfoliation yield of 100%. The WS2-anodes enable DIBs, based on hexafluorophosphate (PF6-) and lithium (Li+) ions, to achieve charge specific capacities of 457, 438, 421, 403, 295 and 169 mAh g-1 at current rates of 0.1, 0.2, 0.3, 0.4, 0.8 and 1.0 A g-1, respectively, outperforming convent…
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…
