Synthesis and characterization of single-crystalline alpha-MoO3 nanofibers for enhanced Li-ion intercalation applications

High quality, single-crystalline alpha-MoO3 nanofibers are synthesized by rapid hydrothermal method using a polymeric nitrosyl-complex of molybdenum(II) as molybdenum source without employing catalysts, surfactants, or templates. The possible reaction pathway is decomposition and oxidation of the complex to the polymolybdate and then surface condensation on the energetically favorable 001] direction in the initially formed nuclei of solid alpha-MoO3 under hydrothermal conditions. Highly crystalline alpha-MoO3 nanofibers have grown along 001] with lengths up to several micrometres and widths ranging between 280 and 320 nm. The alpha-MoO3 nanofibers exhibit desirable electrochemical properties such as high capacity reversibility as a cathode material of a Li-ion battery.

Thermodynamic aspects of ion intercalation in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: Application to the Everit's salt/Prussian Blue transition

The K+ reversible processes for ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K+ ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.

Irreversible capacity loss of graphite electrode in lithium-ion batteries

The irreversible capacity loss of the carbon electrode in lithium-ion batteries at the first cycle is caused mostly by surface film growth. We inspected an unknown irreversible capacity loss (UICL) of the natural graphite electrodes. The charge/discharge behavior of graphite and meso-phase carbon microbeads heat-treated at 2800 degrees C (MCMB28) as the materials of the carbon anode in the lithium-ion battery were compared. It was found that the capacity loss of the natural graphite electrode in the first cycle is caused not only by surface film growth, but also by irreversible lithium-ion intercalation on the new formed surface at the potential range of lithium intercalation, while the capacity loss of the MCMB28 electrode is mainly originated from surface film growth. The reason for the difference of their irreversible capacity losses of these two kinds of carbon material was explained in relation to their structural characteristics. (C) 1997 Published by Elsevier Science S.A.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM) and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a inter-penetrating bilayer model in the gallery of LDH, with 49o tilting angle. Yet Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm-1, assigned to the combination result of the N-H stretching vibrations, which was considered as a mark to assess MO- ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a “honey-comb” like structure. Yet the Ca/Al-LDH-GR maintained regular hexagons platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO- ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorped upon Ca/Al-LDH-Cl surfaces.

High performance electrochromic devices based on anodized nanoporous Nb2O5

Despite the predictions, the true potential of Nb2O5 for electrochromic applications has yet to be fully realized. In this work, three-dimensional (3D) compact and well-ordered nanoporous Nb2O5 films are synthesized by the electrochemical anodization of niobium thin films. These films are formed using RF sputtering and then anodized in an electrolyte containing ethylene glycol, ammonium fluoride, and small water content (4%) at 50 °C which resulted in low embedded impurities within the structure. Characterization of the anodized films shows that a highly crystalline orthorhombic phase of Nb2O5 is obtained after annealing at 450 °C. The 3D structure provides a template consisting of a large concentration of active sites for ion intercalation, while also ensuring low scattering directional paths for electrons. These features enhance the coloration efficiency to 47.0 cm2 C?1 (at 550 nm) for a 500 nm thick film upon Li+ ion intercalation. Additionally, the Nb2O5 electrochromic device shows a high bleached state transparency and large optical modulation.

Removal of methyl orange from aqueous solutions through adsorption by calcium aluminate hydrates

Methyl orange (MO) is a kind of anionic dye and widely used in industry. In this study, tricalcium aluminate hydrates (Ca-Al-LDHs) are used as an adsorbent to remove methyl orange (MO) from aqueous solutions. The resulting products were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), thermal analysis (TG-DTA) and scanning electron microscope (SEM). The XRD results indicated that the MO molecules were successfully intercalated into the tricalcium aluminate hydrates, with the basal spacing of Ca-Al-LDH expanding to 2.48 nm. The MIR spectrum for CaAl-MO-LDH shows obvious bands assigned to the N@N, N@H stretching vibrations and S@O, SO_ 3 group respectively, which are considered as marks to assess MO_ ion intercalation into the interlayers of LDH. The overall morphology of CaAl-MOLDH displayed a ‘‘honey-comb’’ like structure, with the adjacent layers expanded.

V(2)O(5)-Anchored Carbon Nanotubes for Enhanced Electrochemical Energy Storage

Functionalized multiwalled carbon nanotubes (CNTs) are coated with a 4-5 nm thin layer of V(2)O(5) by controlled hydrolysis of vanadium alkoxide. The resulting V(2)O(5)/CNT composite has been investigated for electrochemical activity with lithium ion, and the capacity value shows both faradaic and capacitive (nonfaradaic) contributions. At high rate (1 C), the capacitive behavior dominates the intercalation as 2/3 of the overall capacity value out of 2700 C/g is capacitive, while the remaining is due to Li-ion intercalation. These numbers are in agreement with the Trasatti plots and are corroborated by X-ray photoelectron spectroscopy (XPS) studies on the V(2)O(5)/CNTs electrode, which show 85% of vanadium in the +4 oxidation state after the discharge at 1 C rate. The cumulative high-capacity value is attributed to the unique property of the nano V(2)O(5)/CNTs composite, which provides a short diffusion path for Lit-ions and an easy access to vanadium redox centers besides the high conductivity of CNTs. The composite architecture exhibits both high power density and high energy density, stressing the benefits of using carbon substrates to design high performance supercapacitor electrodes.

Synthesis and Electrochemical Characterization of LiNi0.8Co0.2O2 as Cathode Material for Aqueous Rechargeable Lithium Batteries

LiNi0.8Co0.2O2 cathode material for lithium ion batteries is synthesized by reaction under autogenic pressure at elevated temperature (RAPET) method. The simple synthesis procedure is time and energy saving, and thus is promising for commercial application. The structure and stability of the material have been characterized by means of XRD and TG-DTA. The electrochemical properties of the LiNi0.8Co0.2O2 cathode are investigated in 2 M Li2SO4 aqueous electrolyte and they are compared to that in an organic electrolyte. A battery cell consisting of LiNi0.8Co0.2O2 as cathode in 2 M Li2SO4 solution is constructed in combination with LiTi2 (PO4)(3) as anode. The cell retained almost constant discharge capacity over hundred cycles. The electrochemical impedance spectral ( EIS) studies in aqueous and nonaqueous electrolytes revealed that the mechanism of lithium ion intercalation and deintercalation processes in LiNi0.8Co0.2O2 electrode follow almost similar mechanism in both aqueous and nonaqueous electrolytes. The chemical diffusion coefficient was calculated from slow scan rate cyclic voltammetry and EIS. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.075205jes] All rights reserved.

Electrochemical exfoliation of graphite to produce graphene using tetrasodium pyrophosphate

An electrochemical exfoliation based synthetic methodology to produce graphene is provided. An eco-friendly and non-toxic tetrasodium pyrophosphate solution in which the pyrophosphate anion acts as an intercalating ion was used as the electroactive media. Five different ion intercalation potentials were used. Characterization by microscopy, X-ray diffraction, Raman spectroscopy and UV-Visible spectroscopic techniques confirmed that all the potentials produced nano to micrometer sized graphene sheets. No trace of graphene oxide was detected. It was observed that (i) an increase in the intercalation potential increased the graphene yield and (ii) the defect density of graphene did not change significantly with a change in the intercalation potential.

AILaNb2O7:A new series of layered perovskites exhibiting ion exchange and intercalation behaviour

A new series of layered perovskite oxides, AILaNb2O7 (A = Li, Na, K, Rb, Cs, NH4) constituting n = 2 members of the family A A′n−1BnO3n+1, has been prepared. Their structure consists of double perovskite slabs interleaved by A atoms. Hydrated HLaNb2O7 is formed by topotactic proton exchange of the A atoms in ALaNb2O7 (A = K, Rb, Cs). The hydrate readily loses water to give anhydrous HLaNb2O7 which is isostructural with RbLaNb2O7. HLaNb2O7 exhibits Bronsted acidity forming intercalation compounds with bases such as n-octylamine and pyridine.

HNbWO6 and HTaWO6: Novel layered oxides related to the rutile structure. Synthesis and investigation of ion-exchange and intercalation behaviour

New protonated layered oxides, HMWO6·1.5H2O (M=Nb or Ta), have been synthesized by topotactic exchange of lithium in trirutile LiMWO6 with protons by treatment with dilute HNO3. The tetragonal cell constants are a=4.71 (2) and c=25.70 (8)Å for HNbWO6·1.5H2O and a=4.70 (2) and c=25.75 (9) Å for HTaWO6·1.5H2O. Partially hydrated compounds, HMWO6·0.5H2O and anhydrous compounds, HMWO6 retain the layered structure. The structure of these oxides consists of MWO6 sheets built up of M/W-oxygen octahedra with rutile type corner- and edge-sharing. Interlayer protons in HMWO6 are exchanged with Li+, Na+, K+ and Tl+. HMWO6 exhibit Brønsted acidity intercalating n-alkylamines and pyridine.

ChemInform Abstract: Synthesis of Anion-Deficient Layered Perovskites, ACa2Nb3-xMxO10-x (A: Rb, Cs; M: Al, Fe), Exhibiting Ion-Exchange and Intercalation. Evidence for the Formation of Layered Brownmillerites, ACa2Nb2AlO9 (A: Cs, H)

Anion-deficient layered perovskite oxides of the formula, ACa2Nb3-xMxO10-x (A = Rb, Cs; M = Al, Fe) for 0 < x less-than-or-equal-to 1.0, possessing tetragonal structures similar to the parent ACa2Nb3O10, have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO3 to give the protonated derivatives, HCa2Nb3-xMxO10-x; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK(a) = 4.63). The distribution of acid sites in the interlayer region of HCa2Nb2MO9 inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa2Nb2MO9 samples prepared at 1100-1200-degrees-C. Annealing a disordered sample of CsCa2Nb2AlO9 for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO6/2)-tetrahedral (AlO4/2)-octahedral (NbO6/2) layer sequence reminiscent of the brownmillerite structure.

Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry

Positive and negative ion electrospray ionization (ESI) mass spectra of complexes of positively charged small molecules (distamycin, Hoechst 33258, [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2) have been compared. [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2 bind to DNA by intercalation. Negative ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA showed ions from DNA-ligand complexes consistent with solution studies. In contrast, only ions from freeDNAwere present in positive ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA, highlighting the need for obtaining ESI mass spectra of non-covalent complexes under a range of experimental conditions. Negative ion spectra of mixtures of the minor groove binder Hoechst 33258 with DNA containing a known minor groove binding sequence were dominated by ions from a 1:1 complex. In contrast, in positive ion spectra there were also ions present from a 2:1 (Hoechst 33258: DNA) complex, suggesting an alternative binding mode was possible either in solution or in the gas phase. When Hoechst 33258 was mixed with a DNA sequence lacking a high affinity minor groove binding site, the negative ion ESI mass spectra showed that 1:1 and 2:1 complexes were formed, consistent with existence of binding modes other than minor groove binding. The data presented suggest that comparison of positive and negative ion ESI-MS spectra might provide an insight into various binding modes in both solution and the gas phase.