Preparation and Structural Investigation of CuCl_2 Graphite Intercalation Compounds

Superfine graphite powder was prepared by ball-milling exfoliated graphite containing anhydrous CuCl2 in planetary ball milling systems. Nano-scale CuCl2 graphite intercalation compounds were synthesized by heating a mixture of anhydrous CuCl2 and graphite nanosheets. Scanning electron microscopy, energy-dispersive X-ray spectroscopy and high-resolution transmission electron microscopy were performed to characterize the microstructures of stage-1 nano-scale CuCl2 graphite intercalation compounds. The structure and components of the domain wall and core in the nano-scale CuCl2 graphite intercalation compounds are described. The results show that the content of CuCl2 in the mixture plays a crucial role in the size of the nano-scale CuCl2 graphite intercalation compound.

Electrical Properties of Expanded Graphite Intercalation Compounds

The intercalation compounds of CuCl2 were synthesized with expanded graphite, whose magni-tude of the electrical conductivity is about 103S.cm1. Their electrical conductivity is 3-6 times as high as that of the expanded graphite, and about 10 times as high as that of GIC made of the non-expanded graphite. The microanalysis results of chemical compounds by X-ray energy spectrum scanning of TEM testified that the atomic ratio of chloride and cupric is nonstoichoi-metric. The multivalence and exchange of electrovalence of the cupric ion was confirmed by the XPS-ESCA. Vacancy of chlorine anion increases the concentration of charge carrier. The special stage structure, made of graphite and chloride, produces a weak chemical bond belt and provides a carrier space in the direction of GIC layer. These factors develop the electrical properties.

Synthesis of NdCl_3-FeCl_3-Graphite Intercalation Compounds

NdCl3-FeCl3-graphite intercalation compounds were synthesized by means of molten salt-exchange method.Their layer structure and the relative content of the elements were investigated by X-ray diffraction, scanning electronmicroscopy and energy dispersive X-ray spectroscopy. The results show that the products are mixtures of 2, 3,4-stages,among them, the c-axis repeat distance, Ic, of stage-3 NdCl3-GIC is 1. 6536±0. 0024 nm. In addition, the mechanismof RECl3 intercalation reaction was discussed.

Study of NdCl_3-FeCl_3-Graphite Intercalation Compounds by X-Ray Photoelectron Spectroscopy

NdCl 3 FeCl 3 graphite intercalation compounds were synthesized by molten salt exchange method. The state of the intercalates and the relative contents of Nd, Fe, Cl, C in the product were determined by X ray photoelectron spectroscopy(XPS). From the XPS data, it is concluded that the binding energy of Fe2p electrons is about 711 20～710 3 eV, the binding energy of Nd3d electrons is about 983 08～983 20 eV, and Fe in the product has two valence states (Fe 3+ and Fe 2+ ).

A PRELIMINARY STUDY ON THE STABILITY OF TERNARY CoCl_2-FeCi_3 GRAPHITE INTERCALATION COMPOUNDS

The ternary CoCl2-FeCl3 graphite intercalation compounds (CoCl2-FeCl3 G/C) have been subjected to different treatments in various media. It is found that the CoCl2-FeCl3 GIC is stable 'when it is stored under conditions of opening to at-mosphere,whereas,acids,NaOH,boiling water,and heat treat-ments have different effects on the stability of the CoCl2-FeCl3 G/C.

Computer simulation of order-disorder phase transition in the intercalation compounds M_(1/2)TiS_2 (M=Fe, Co, Ni)

Based on cluster variation method (CVM) and natural iteration method (MM),order-disorder phase transition in the intercalation compounds M_(1/2)TiS_2 is simulated bycomputer. The favorable conditions, under which 3^(1/2)a_0 x a_0 superstructure is formed, aregiven, and the results are in good agreement with the experiments and theoretical calculations. Therelationship between critical temperature and M-ion-vacancy interaction parameter is linear.

Intercalation of multiply solvated hexafluorophospate anion into graphite electrode from mixtures of methyl acetate,ethyl methyl and ethylene carbonates

Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.

Doping inhomogeneity and staging of ultra-thin graphite intercalation compound flakes probed by visible and near-infrared Raman spectroscopy

When ultra-thin graphite intercalation compounds（GICs） are deposited on the SiO2/Si substrate, it is found that their colors are dependent on the thickness of GIC flakes. The sample colors of ultrathin GIC flakes can no longer provide qualitative information on the stage index. Here, multi-wavelength Raman spectroscopy is thus applied to study the doping inhomogeneity and staging of ultra-thin GICs by FeCl3 intercalation. The G band intensity of stage-1 GIC flakes is strongly enhanced by 532-nm laser excitation, while that of stage-2 and stage-3 flakes exhibits strong intensity enhancement for 785-nm laser excitation. The near-infrared lasers are suggested to probe the doping inhomogeneity and staging of ultra-thin GIC flakes.

Electronic Effect of Carbon Support on Pt Catalyst Supported on Graphite Intercalation Compound

Graphite intercalation compounds（GIC） were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fuel cells. The GIC samples with different intercalation degrees were prepared by electrolyzing graphite flake in H2SO4 for varying the periods of time. The GIC-supported Pt catalyst was deposited electrochemically. The catalytic activity and poisoning tolerance of the GIC-supported Pt catalysts were evaluated. It was found that GIC with sulfate anion as intercalate was able to catalyze methanol electrooxidation, which could be related to the positive charges generated on the graphite layer upon intercalation. As intercalation degree increased, the catalytic activity of the GIC-supported Pt catalyst decreased while the poisoning tolerance improved. This suggests that electron donation from support to catalyst had great effect on both catalytic activity and poisoning tolerance of Pt catalyst. And intercalation can be adopted as another important way to make modification on carboneous catalyst support.

STUDY ON THE MICROSTRUCTURE OF Fe-KCI GRAPHITE INTERCALATION COMPOUND

The intercalatants presence of Fe-KCl graphite intercalation compound (Fe-KCl G/C) is in the form of independent crystalline phase. In this paper, its distribution in the carbon interlayer, crystalline status and powder sizes have been studied by X-ray diffraction (XRD) , small angle X-ray scattering (SAXS) and transmission electron microscope (TEM). And the partial crystal structure of the GIC has been researched too.

Electrochemically triggered decoupled transport behaviors in intercalated graphite:From energy storage to enhanced electromagnetic applications

Pyrolytic graphite (PG) with highly aligned graphene layers,present anisotropic electrical and thermal transport behavior,which is attractive in electronic,electrocatalyst and energy storage.Such pristine PG could meeting the limit of electrical conductivity (~2.5×10^(4) S·cm^(−1)),although efforts have been made for achieving high-purity sp^(2) hybridized carbon.For manipulating the electrical conductivity of PG,a facile and efficient electrochemical strategy is demonstrated to enhance electrical transport ability via reversible intercalation/de-intercalation of AlCl_(4)^(-)into the graphitic interlayers.With the stage evolution at different voltages,variable electrical and thermal transport behaviors could be achieved via controlling AlCl_(4)^(-)concentrations in the PG because of substantial variation in the electronic density of states.Such evolution leads to decoupled electrical and thermal transport (opposite variation trend) in the in-plane and out-of-plane directions,and the in-plane electrical conductivity of the pristine PG (1.25×10^(4) S·cm^(−1)) could be massively promoted to 4.09×10^(4) S·cm(AlCl_(4)^(-)intercalated PG),much better than the pristine bulk graphitic papers used for the electrical transport and electromagnetic shielding.The fundamental mechanism of decoupled transport feature and electrochemical strategy here could be extended into other anisotropic conductive bulks for achieving unusual behaviors.

Localized-domains staging structure and evolution in lithiated graphite

Intercalation provides to the host materials a means for controlled variation of many physical/chemical properties and dominates the reactions in metal‐ion batteries.Of particular interest is the graphite intercalation compounds with intriguing staging structures,which however are still unclear,especially in their nanostructure and dynamic transition mechanism.Herein,the nature of the staging structure and evolution of the lithium(Li)‐intercalated graphite was revealed by cryogenic‐transmission electron microscopy and other methods at the nanoscale.The intercalated Li‐ions distribute unevenly,generating local stress and dislocations in the graphitic structure.Each staging compound is found macroscopically ordered but microscopically inhomogeneous,exhibiting a localized‐domains structural model.Our findings uncover the correlation between the long‐range ordered structure and short‐range domains,refresh the insights on the staging structure and transition of Li‐intercalated/deintercalated graphite,and provide effective ways to enhance the reaction kinetic in rechargeable batteries by defect engineering.

Synthesis and characterization of Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3-coated LiMn_2O_4 by wet chemical route

Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 was prepared by wet chemical route. The phase,surface morphology,and electrochemical properties of the prepared powders were characterized by X-ray diffraction,scanning electron micrograph,and galvanostatic charge-discharge experiments. Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 has similar X-ray diffraction patterns as LiMn2O4. The corner and border of Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 particles are not as clear as the uncoated one. The two powders show similar values of lithiumion diffusion coefficient. When cycled at room temperature and 55°C for 40 times at the charge-discharge rate of 0.2C,Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 shows the capacity retentions of 98.2% and 93.9%,respectively,which are considerably higher than the values of 85.4% and 79.1% for the uncoated one. Both the capacity retention differences between Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 and LiMn2O4 cycling at room temperature and 55°C become larger with the increase of charge-discharge rate. When the charge-discharge rate reaches 2C,the capacity retention of LATP-coated LiMn2O4 becomes 8.4% higher than the uncoated LiMn2O4 for room temperature cycling,and it becomes 11.1% higher than the latter when cycled at 55°C.

Characteristics and Microstructure of Graphite Encapsulated Iron Nanoparticles

The graphite encapsulated a-Fe particles were prepared by reduction of stage-2 and stage-3 FeCI3 graphite intercalation compounds （GICs） with metallic potassium, X-ray diffraction analysis （XRD）, energy dispersive X-ray spectroscopy （EDS） investigation and transmission electron microscopy （TEM） observation show that the reduction products of stage-2 FeCl3-GICs contains more abundant a-Fe nanoparticles than those of stage-3. High-resolution TEM （HRTEM） observation reveals that the nanoparticle of a-Fe was polycrystals or twins, which was real or quasi two-dimension in shape, and whose space orientation was strictly controlled by the graphene. Based on the experiment results, a possible growth model of the graphite encapsulated ct-Fe was proposed.

Intercalation behavior of spiro-bipyrrolidinium cation into graphite electrodes from ethylene carbonate

The intercalation behavior of spiro-(1,1)-bipyrrolidinium cation(SBP+) into graphite electrode from spiro-(1,1)-bipyrrolidinium tetrafluoroborate-ethylene carbonate(SBPBF4-EC) solutions is investigated by conventional electrochemical tests and in situ X-ray diffraction measurements. Two kinds of graphite intercalation compounds(GICs) with discrete characteristic intercalated gallery heights(IGHs)(ca. 0.95 and0.75 nm) can be obtained with varying the salt concentration. The effect of graphite type is also addressed.

Preparation of Chinese fir wood/MMT nanocomposites and the factors affecting it

The nano intercalation compounding of wood and MMT has important implications for the modification of wood and for the development of new materials. With water-soluble phenol formaldehyde resin as an intermediary, the nanocomposites of Chinese fir （Cunningharnia lanceolata） wood and montmorillonite （MMT） were prepared via three impregnation methods, i.e. normal pressure, once and twice vacuum methods. Based on the weight percent gain （WPG） of impregnated wood, the effects of compounding wood and MMT in terms of concentration, impregnating temperature and time, wood moisture content and wood extraction treatments, on sapwood and heartwood are discussed. Results show that： 1） the optimum MMT concentration in the impregnation solution is 3% for sapwood and 5% for heartwood; 2） room temperature is suitable in practice; 3） treatment pressure should be set at a high enough value in order to ensure sufficient permeation; 4） the effects of different impregnation methods on sapwood and heartwood are different, the heartwood extractives affect WPG significantly; cell wall permeability of sapwood is better than that of heartwood; 5） the cold water, hot water and benzene-ethanol solution extractions can all greatly improve the permeability of heartwood, hot water can dissolve some hemicellulose of low aggregation and hot water extraction improves wood cell wall permeability; 6） with an increase in wood moisture content, the permeable space in wood is reduced, but with a certain amount of water, instantaneous spaces are created and the permeation dynamic increases. This effect is especially apparent for difficult impregnating situations in heartwood and impregnation under normal pressure.

Preparation and characterization of wood/montmorillonite nanocomposites

With montmorillonite （MMT） organically modified as organophilic MMT （OMMT） and water-soluble phenol formaldehyde resin （PF） as intermediate, Chinese fir （Cunningharnia lanceolata） wood/MMT nanocomposites （WMNC） were prepared via nano intercalation compounding and characterized by XRD, SEM and FTIR. Results show that： 1） the preparation of OMMT is very successful; 2） the self-made PF can effectively intercalate into MMT to increase markably its gallery distance and even exfoliate its nano silicate laminae; 3） the XRD analysis indicates that some exfoliated MMT enters the non-crystallized region of microfibrils in wood cell walls and the crystallinity degree of wood in WMNC decreases; 4） the SEM graphs show that multiform MMT exists in WMNC. Some grains block in wood cell lumen, some layers adhere to the wood surface of the inner cell wall and some exfoliated nanolaminae even insert into wood cell walls; and 5） the FTIR analysis suggests that MMT and wood in WMNC perhaps interact via certain chemical bonding.