Lithium intercalation via -Butyllithium of the layered transition metal dichalcogenides

Dines, Martin B.

doi:10.1016/0025-5408(75)90115-4

Cited by 391 publications

(229 citation statements)

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“…The intercalation of TMDCs by ionic species [46][47][48][49][50][51] allows the layers to be exfoliated in liquid. The intercalation method was first demonstrated in the 1970s (ref.…”

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confidence: 99%

“…The intercalation method was first demonstrated in the 1970s (ref. 51) and the subsequent exfoliation into thin layers by Morrison, Frindt and co-workers in the 1980s (ref. 47), and these methods are experiencing renewed interest today 49,50 .…”

mentioning

confidence: 99%

“…The intercalation of TMDCs by lithium was demonstrated in the 1970s (ref. 51), and the intercalation-driven exfoliation was first advanced by Morrison, Frindt and co-workers 47 . The typical procedure involves submerging bulk TMDC powder in a solution of a lithium-containing compound such as n-butyllithium for more than a day to allow lithium ions to intercalate, followed by exposing the intercalated material to water.…”

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confidence: 99%

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Electronics and optoelectronics of two-dimensional transition metal dichalcogenides

et al. 2012

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699M any two-dimensional (2D) materials exist in bulk form as stacks of strongly bonded layers with weak interlayer attraction, allowing exfoliation into individual, atomically thin layers 1 . The form receiving the most attention today is graphene, the monolayer counterpart of graphite. The electronic band structure of graphene has a linear dispersion near the K point, and charge carriers can be described as massless Dirac fermions, providing scientists with an abundance of new physics 2,3 . Graphene is a unique example of an extremely thin electrical and thermal conductor 4 , with high carrier mobility 5 , and surprising molecular barrier properties 6,7 .Many other 2D materials are known, such as the TMDCs 8,9 , transition metal oxides including titania-and perovskite-based oxides 10,11 , and graphene analogues such as boron nitride (BN) 12,13 . In particular, TMDCs show a wide range of electronic, optical, mechanical, chemical and thermal properties that have been studied by researchers for decades 9,14,15 . There is at present a resurgence of scientific and engineering interest in TMDCs in their atomically thin 2D forms because of recent advances in sample preparation, optical detection, transfer and manipulation of 2D materials, and physical understanding of 2D materials learned from graphene.The 2D exfoliated versions of TMDCs offer properties that are complementary to yet distinct from those in graphene. Graphene displays an exceptionally high carrier mobility exceeding 10 6 cm 2 V -1 s -1 at 2 K (ref. 16) and exceeding 10 5 cm 2 V -1 s -1 at room temperature for devices encapsulated in BN dielectric layers 5 ; because pristine graphene lacks a bandgap, however, fieldeffect transistors (FETs) made from graphene cannot be effectively switched off and have low on/off switching ratios. Bandgaps can be engineered in graphene using nanostructuring [17][18][19] , chemical functionalization 20 and applying a high electric field to bilayer graphene 21 , but these methods add complexity and diminish mobility. In contrast, several 2D TMDCs possess sizable bandgaps around 1-2 eV (refs 9,14), promising interesting new FET and optoelectronic devices.TMDCs are a class of materials with the formula MX 2 , where M is a transition metal element from group IV (Ti, Zr, Hf and so on), group V (for instance V, Nb or Ta) or group VI (Mo, W and so on), and X is a chalcogen (S, Se or Te). These materials form layered structures of the form X-M-X, with the chalcogen atoms in two hexagonal planes separated by a plane of metal atoms, as shown in Fig. 1a. Adjacent layers are weakly held together to form the bulk crystal in a variety of polytypes, which vary in stacking orders and metal atom coordination, as shown in Fig. 1e. The overall symmetry of TMDCs is hexagonal or rhombohedral, and the metal atoms have octahedral or trigonal prismatic coordination. The electronic properties of TMDCs range from metallic to semiconducting, as summarized in Table 1. There are also TMDCs that exhibit exotic behaviours such as charge density waves ...

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“…The intercalation of TMDCs by ionic species [46][47][48][49][50][51] allows the layers to be exfoliated in liquid. The intercalation method was first demonstrated in the 1970s (ref.…”

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confidence: 99%

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confidence: 99%

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confidence: 99%

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Electronics and optoelectronics of two-dimensional transition metal dichalcogenides

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“…Another important reason why 2D solids are investigated is their ability to intercalate a large variety of compounds. [1][2][3][4][5][6][7][8][9] In this context, physical properties such as electrical conductivity and electrochemical behavior of layered solids can be deliberately modified by intercalation of organic species. [2][3][4]10,11 Among different 2D solids, the study of layered transition-metal dichalcogenides (LTMDs) has become the subject of an active field of research in solid state physics and chemistry during the last decades.…”

Section: Introductionmentioning

confidence: 99%

“…21 An alternative route, mainly applied to MoS 2 , consists in the use of intermediate lithiated phases prepared by lithium chemical insertion using n-butyl lithium (n-BuLi). 6,7 These intermediate compounds are able to react with water producing colloidal dispersions due to the exfoliation of the dichalcogenide in elemental lamellae. In a further restacking process, these lamellae can entrap molecular or polymeric species present in the dispersion.…”

Section: Introductionmentioning

confidence: 99%

Intercalation and electrical behavior of Ta xMo1-xS2 (x > 0.5) layered mixed disulfides

Lara¹,

Ruiz²,

Manrı́quez³

et al. 2012

J. Braz. Chem. Soc.

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Este trabalho relata um estudo sistemático do comportamento estrutural e elétrico de três fases ternárias do sistema Ta x Mo 1-x S 2 (x = 0,55, 0,75 e 0,90) e de seus compostos de intercalação resultantes das inserções química e eletroquímica de lítio, assim como das intercalações de piridina e poli(óxido de etileno). As três fases foram preparadas pela reação direta de seus elementos constituintes, sem qualquer outro aditivo, a 900 o C em atmosfera inerte. Os compostos resultantes foram caracterizados por meio de difratometria de raios X de pó (XRD), análises termogravimétrica e térmica diferencial (TGA/DTA), fluorescência de raios X por dispersão de energia (EDX) e microscopia eletrônica de varredura com emissão de campo (FE-SEM). A condutividade elétrica dos diferentes compostos preparados foi medida no intervalo de temperatura 1,5-300 K utilizando o método convencional de sonda de quatro pontas van der Pauw na presença de um campo magnético de 9 T para verificar a ocorrência do fenômeno de magnetoresistividade.This work reports a systematic study of the structural and electrical behavior of three ternary phases of the Ta x Mo 1-x S 2 system (x = 0.55, 0.75 and 0.90) and their intercalation compounds resulting from both chemical and electrochemical lithium insertions, as well as from pyridine and poly(ethylene oxide) intercalations. The three ternary phases were prepared by direct reaction of their constituting elements, without any other additive, at 900 ºC in inert atmosphere. The resulting compounds were characterized by means of X-ray powder diffractometry (XRD), thermogravimetric and differential thermal (TGA/DTA) analyses, energy dispersive X-ray fluorescence (EDX) and field emission-scanning electron microscopy (FE-SEM). The electrical conductivity of the different products was measured in the 1.5-300 K temperature range using the conventional four probe van der Pauw method in the presence of a 9 T magnetic field in order to verify the occurrence of magnetoresistivity phenomena. Keywords: chalcogenides, intercalation, pyridine, PEO, conductivity IntroductionThe renewed interest to study layered solids is originated from the observation of unusual physical properties associated with anisotropy phenomena in such type of low-dimensional materials. Another important reason why 2D solids are investigated is their ability to intercalate a large variety of compounds. [1][2][3][4][5][6][7][8][9] In this context, physical properties such as electrical conductivity and electrochemical behavior of layered solids can be deliberately modified by intercalation of organic species. [2][3][4]10,11 Among different 2D solids, the study of layered transition-metal dichalcogenides (LTMDs) has become the subject of an active field of research in solid state physics and chemistry during the last decades. 1,12,13 One of the most salient physical properties of these materials is their electrical conductivity (and superconductivity) behavior, which is related to phase transitions usually driven by charge density wave mechanisms...

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Intercalation Chemistry

Jacobson

Nazar

2005

Encyclopedia of Inorganic Chemistry

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The term ‘intercalation’ refers to a process whereby a guest molecule or ion is inserted into a host lattice. The structure of the guest–host or intercalation compound is only slightly perturbed from the host structure and the reaction used to form the compound is reversible. In this chapter, the major classes of host lattice are classified by both dimensionality and electronic properties. In three‐dimensional systems, the sizes of the guest species are constrained by the dimensions of the host lattice. In lower dimensional systems, no such restriction exists and the strongly bonded layers or chains can adjust their separation freely to accommodate guest species of different sizes. With increasing guest size, the structural correlation between layers or chains is diminished and in the limiting case, complete separation of single layers or chains occurs in solution, resulting in the formation of colloidal dispersions. Insulating host lattices undergo reactions that involve ion exchange, acid–base chemistry, solvent exchange, and sorption of neutral molecules from the gas phase. The insulating hosts have a fixed concentration of ionic guests that remains unchanged throughout subsequent reactions. The conducting host lattices have the feature that the concentration of ionic guest species can be altered by oxidation or reduction of the host. The chemistry of most compounds involves reduction and cation intercalation with the major exceptions of graphite and some layered oxides, which can be both reductively intercalated with cations and oxidized with anion insertion. The present understanding of the mechanism of intercalation with particular emphasis on layered structures is reviewed. Reactions involve adsorption of guest species on host crystals, exchange or insertion at the host surface, the formation of intermediate stages in layered compounds, and transport within the host lattice. Macroscopic effects such as variations in crystal size, dislocations, stacking faults, and pore mouth blockage can strongly influence the reaction kinetics. The major classes of host lattices in each category and their chemical behavior are described. The insulating materials discussed include zeolites, clays, layered double hydroxides, acid phosphates, and layered oxides while graphite, C 60 , carbon nanotubes, transition metal chalcogenides, metal phosphorus trisulfides, metal oxyhalides, metal nitride halides, and metal oxides are the major examples of conducting hosts. In the case of metal oxides, examples of both reductive intercalation of lithium ions and oxidative intercalation of oxide ions are discussed. These two types of intercalation reactions are important for lithium batteries and high‐temperature superconductivity, respectively.

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Lithium intercalation via -Butyllithium of the layered transition metal dichalcogenides

Cited by 391 publications

References 4 publications

Electronics and optoelectronics of two-dimensional transition metal dichalcogenides

Electronics and optoelectronics of two-dimensional transition metal dichalcogenides

Intercalation and electrical behavior of Ta xMo1-xS2 (x > 0.5) layered mixed disulfides

Intercalation Chemistry

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