A novel anode material of antimony nitride for rechargeable lithium batteries

Antimony nitride thin film has been successfully fabricated by magnetron sputtering method and its electrochemistry with lithium was investigated for the first time. The reversible discharge capacity of Sb₃N/Li cells cycled between 0.3 V and 3.0 V was found above 600 mAh/g. By using transmission electron microscopy and selected area electron diffraction measurements, the conversion reaction of Sb₃N into Li₃Sb and Li₃N was revealed during the lithium electrochemical reaction of Sb₃N thin film electrode. The high reversible capacity and the good cycleability made Sb₃N one of promising anode materials for future rechargeable lithium batteries.     

Direct electrochemistry of glucose oxidase based on its direct immobilization on carbon ionic liquid electrode and glucose sensing

Direct electrochemistry of glucose oxidase (GOx) has been achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1-butyl pyridinium hexafluophosphate ([BuPy][PF₆]) as binder for the first time. A pair of reversible peaks is exhibited on GOx/CILE by cyclic voltammetry. The peak-to-peak potential separation (ΔE_P) of immobilized GOx is 0.056 V in 0.067 M phosphate buffer solution (pH 6.98) with scan rate of 0.1 V/s. The average surface coverage and the apparent Michaelis–Menten constant are 6.69 × 10⁻¹¹ mol·cm⁻² and 2.47 μM. GOx/CILE shows excellent electrocatalytic activity towards glucose determination in the range of 0.1–800 μM with detection limit of 0.03 μM (S/N = 3). The biosensor has been successfully applied to the determination of glucose in human plasma with the average recoveries between 95.0% and 102.5% for three times determination. The direct electrochemistry of GOx on CILE is achieved without the help of any supporting film or any electron mediator. GOx/CILE is inexpensive, stable, repeatable and easy to be fabricated.     

In situ chemical synthesis of SnO2–graphene nanocomposite as anode materials for lithium-ion batteries

An in situ chemical synthesis approach has been developed to prepare SnO₂–graphene nanocomposite. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (4–6 nm in size) on graphene matrix. The electrochemical reactivities of the SnO₂–graphene nanocomposite as anode material were measured by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂–graphene nanocomposite exhibited a reversible lithium storage capacity of 765 mAh/g in the first cycle and an enhanced cyclability, which can be ascribed to 3D architecture of the SnO₂–graphene nanocomposite.     

Goethite nanorods as anode electrode materials for rechargeable Li-ion batteries

Although various transition metal oxides have been reported to act as low potential Li insertion hosts, the oxyhydroxides have remained unexplored to date. We show here that the hydroxide ions present in transition metal oxyhydroxides do not interfere with the lithium uptake and extraction, permitting very good reversibility of the reduction/oxidation reactions. Goethite (α-FeOOH) nanocrystals can uptake and extract large amount of Li via the conversion reaction mechanism, providing a reversible capacity of 500 mA h g⁻¹ at an average potential of 0.85 V vs. Li/Li⁺. The mechanism was examined using a combination of X-ray diffraction, electron microscopy, and the corresponding selected area electron diffractions (SAEDs). The α-FeOOH is reduced into nanoparticles of metallic Fe⁰ embedded in an amorphous matrix of Li₂O and LiOH in the first discharge; the subsequent cyclings are redox reactions between metallic Fe⁰ and Fe₂O₃ clusters.     

Synthesis of magnetic nickel spinel ferrite nanospheres by a reverse emulsion-assisted hydrothermal process

Nickel ferrite nanospheres were successfully synthesized by a reverse emulsion-assisted hydrothermal method. The reverse emulsion was composed of water, cetyltrimethyl ammonium bromide, polyoxyethylene(10)nonyl phenyl ether, iso-amyl alcohol and hexane. During the hydrothermal process, β-FeO(OH) and Ni_0.75Fe_0.25(CO₃)_0.125(OH)₂·0.38H₂O (INCHH) nanorods formed first and then transformed into nickel spinel ferrite nanospheres. The phase transformation mechanism is proposed based on the results of X-ray powder diffraction, transmission electron microscopy and energy-dispersive X-ray spectroscopy, etc. Nickel ferrite may form at the end of the INCHH nanorods or from the solution accompanied by the dissolution of β-FeO(OH) and INCHH nanorods. The X-ray photoelectron spectroscopy analysis shows that a few Fe³⁺ ions have been reduced to Fe²⁺ ions during the formation of nickel ferrite. The maximum magnetization of the nickel ferrite nanospheres obtained after hydrothermal reaction for 30 h is 55.01 emu/g, which is close to that of bulk NiFe₂O₄.     

The phase transition behaviors of Li1−xMn0.5Fe0.5PO4 during lithium extraction studied by in situ X-ray absorption and diffraction techniques

How the structural changes take place in LiMn_yFe_1−yPO₄-type cathode materials during lithium extraction/insertion is an important issue, especially on if they go through the single-phase reaction (i.e., solid solution reaction) or the two-phase reaction regions. Here we report the studies on the phase transition behaviors of a carbon coated Li_1−xMn_0.5Fe_0.5PO₄ (CLi₁₋xMn_0.5Fe0_.5PO₄, 0.0  x  1.0) sample during the first charge using in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques. The combination of in situ XAS and XRD results clearly identify two two-phase coexistence regions at two voltage plateaus of 3.6 (Fe²⁺/Fe³⁺) and 4.2 V (Mn²⁺/Mn³⁺) and a narrow intermediate region which proceeds via single-phase reaction in between two two-phase regions. In addition, simultaneous redox reactions of Fe²⁺/Fe³⁺ and Mn²⁺/Mn³⁺ in the narrow single-phase region are reported and discussed for the first time.     

Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine

The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the Mn^IIIPc⁻²/Mn^IIPc⁻² (E_½ = −0.12 V versus Ag|AgCl) and Mn^IIPc⁻²/Mn^IIPc⁻³ (E_½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the Fe^IIPc⁻²/Fe^IPc⁻² (E_½ = −0.35 V versus Ag|AgCl) and Fe^IPc⁻²/Fe^IPc⁻³ (E_½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to Fe^IIIPc⁻²/Fe^IIPc⁻² (E_½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.     

Nanocrystalline ZnMn2O4 as a novel lithium-storage material

Nanocrystalline ZnMn₂O₄ is prepared by a polymer-pyrolysis route and used as a novel anode for lithium ion batteries. XRD and HRTEM studies reveal that the products are highly phase-pure and 30–60 nm in size. Galvanostatic cycling of ZnMn₂O₄ electrode at 100 mA g⁻¹ (about 0.52 mA cm⁻²) between 0.01 and 3.0 V up to 50 cycles exhibits almost stable cycling performance between 10 and 50 cycles with only an average capacity fade of 0.20% per cycle and the electrode still maintains a capacity of 569 mAh g⁻¹ after 50 cycles.     

Immobilization of flavine adenine dinucleotide onto nickel oxide nanostructures modified glassy carbon electrode: fabrication of highly sensitive persulfate sensor

A simple method was used to fabricate flavin adenine dinucleotide (FAD)/NiOx nanocomposite on the surface of glassy carbon (GC) electrode. Cyclic voltammetry technique was applied for deposition nickel oxide nanostructures onto GC surface. Owing to its high biocompatibility and large surface area of nickel oxide nanomaterials with immersing the GC/NiOx-modified electrode into FAD solution for a short period of time, 10–140 s, a stable thin layer of the FAD molecules immobilized onto electrode surface. The FAD/NiOx films exhibited a pair of well-defined, stable, and nearly reversible CV peaks at wide pH range (2–10). The formal potential of adsorbed FAD onto nickel oxide nanoparticles film, E ^o′ vs. Ag/AgCl reference electrode is −0.44 V in pH 7 buffer solutions was similar to dissolved FAD and changed linearly with a slope of 58.6 mV/pH in the pH range 2–10. The surface coverage and heterogeneous electron transfer rate constant (k _s ) of FAD immobilized on NiOx film glassy carbon electrode are 4.66 × 10⁻¹¹ mol cm⁻² and 63 ± 0.1 s⁻¹, indicating the high loading ability of the nickel oxide nanoparticles and great facilitation of the electron transfer between FAD and nickel oxide nanoparticles. FAD/NiOx nanocomposite-modified GC electrode shows excellent electrocatalytic activity toward S₂O₈²⁻ reduction at reduced overpotential. Furthermore, rotated modified electrode illustrates good analytical performance for amperometric detection of S₂O₈²⁻. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 3 μM–1.5 mM, 0.38 μM and 16.6 nA/μM, respectively.     

X-ray diffraction and Mössbauer spectroscopy studies of LiFe0.5Ti1.5O4 – A new primitive cubic ordered spinel

LiFe_0.5Ti_1.5O₄ was synthesized by solid-state reaction carried out at 900 °C in flowing argon atmosphere, followed by rapid quenching of the reaction product to room temperature. The compound has been characterized by X-ray powder diffraction (XRD) and ⁵⁷Fe Mössbauer effect spectroscopy (MES). It crystallizes in the space group P4₃32, a = 8.4048(1) Å. Results from Rietveld structural refinement indicated 1:3 cation ordering on the octahedral sites: Li occupies the octahedral (4b) sites, Ti occupies the octahedral (12d) sites, while the tetrahedral (8c) sites have mixed (Fe/Li) occupancy. A small, about 5%, inversion of Fe on the (4b) sites has been detected. The MES data is consistent with cation distribution and oxidation state of Fe, determined from the structural data.The title compound is thermally unstable in air atmosphere. At 800 °C it transforms to a mixture of two Fe³⁺ containing phases – a face centred cubic spinel Li_(1+y)/2Fe_(5−3y)/2Ti_yO₄ and a Li_(z−1)/2Fe_(7−3z)/2Ti_zO₅ – pseudobrookite. The major product of thermal treatment at 1000 °C is a ramsdellite type lithium titanium iron(III) oxide, accompanied by traces of rutile and pseudobrookite.     

Field emission of vertically aligned V2O5 nanowires on an ITO surface prepared with gaseous transport

Growing V₂O₅ nanowires (NWs) on a conducting glass substrate combines gaseous transport and pyrolytic deposition of vanadium polyoxometalate anions, and yields vertically aligned vanadium-oxide nanowires. Scanning electron and transmission electron microscopy, selected-area electron diffraction, Raman spectra and powder X-ray analyses indicate that V₂O₅ nanowires as synthesized were single-crystalline and grew anisotropically among direction [010]. NH₂OH·HCl served not only as a reducing agent to produce vanadium polyoxometalate clusters but also as a source of NH₃ gas to facilitate the vapor pyrolysis and deposition. The optical properties of V₂O₅ nanowires exhibit a character dependent on structure. Field emission (FE) measurements show a small turn-on field voltage ~8.3 V/μm, maximum current density 1.8 mA/cm², and a linear Fowler–Nordheim behavior.     

Preparation and characterization of lithium ion-conducting glass-ceramics in the Li1 + xCrxGe2 − x(PO4)3 system

Li₂O–Cr₂O₃–GeO₂–P₂O₅ based glasses were synthesized by a conventional melt-quenching method and successfully converted into glass-ceramics through heat treatment. Experimental results of DTA, XRD, ac impedance techniques and FESEM indicated that Li_1.4Cr_0.4Ge_1.6(PO₄)₃ glass-ceramics treated at 900 °C for 12 h in the Li_1 + xCr_xGe_2 − x(PO₄)₃ (x = 0–0.8) system exhibited the best glass stability against crystallization and the highest ambient conductivity value of 6.81 × 10⁻⁴ S/cm with an activation energy as low as 26.9 kJ/mol. In addition, the Li_1.4Cr_0.4Ge_1.6(PO₄)₃ glass-ceramics displayed good chemical stability against lithium metal at room temperature. The good thermal and chemical stability, excellent conducting property, easy preparation and low cost make it promising to be used as solid-state electrolytes for all-solid-state lithium batteries.     

Hydrothermal synthesis of mesostructured nanocrystalline TiO2 in an ionic liquid–water mixture and its photocatalytic performance

Anatase mesostructured TiO₂ nanocrystalline was prepared in a mixture of 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIM⁺BF₄⁻) ionic liquid and water by a low temperature hydrothermal method. The obtained materials were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and N₂ adsorption–desorption. The existence of BMIM⁺BF₄⁻ enhanced the polycondensation and crystallization rate, which encouraged the formation of anatase crystal. The TiO₂ particles were thermally very stable and thus resistant to anatase-rutile phase transformation during calcination at high temperatures. The anatase TiO₂ showed high photocatalytic activity in the degradation of p-chlorophenol than that of the commercially available TiO₂, Degussa P25. After 2 h reaction under the UV-irradiation of 250 W, the removing rate of p-chlorophenol was up to 96.3%.     

Synthesis and electrochemical properties of Ca-doped LiNi<Subscript>0.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode material for lithium ion battery

LiNi_0.8Co_0.2O₂ and Ca-doped LiNi_0.8Co_0.2O₂ cathode materials have been synthesized via a rheological phase reaction method. X-ray diffraction studies show that the Ca-doped material, and also the discharged electrode, maintains a hexagonal structure even when cycled in the range of 3.0–4.35 V (vs Li⁺/Li) after 100 cycles. Electrochemical tests show that Ca doping significantly improves the reversible capacity and cyclability. The improvement is attributed to the formation of defects caused by the partial occupancy of Ca²⁺ ions in lithium lattice sites, which reduce the resistance and thus improve the electrochemical properties.     

Molecular electrochemistry of hydrofullerenes C70H36—46

Electrochemistry of a mixture of hydrofullerenes C₇₀H_36—46 composed of C₇₀H₃₆, C₇₀H₃₈, C₇₀H₄₄, and C₇₀H₄₆ (50, 20, 14, and 15%, respectively) was studied by cyclic voltammetry in THF and CH₂Cl₂ in the –43—–13 °C temperature range. Two cathodic peaks, namely, one-electron reversible (E° = –3.16 V (Fc^0/+), Fc is ferrocene) and irreversible (E _p = –3.37 V (Fc^0/+)) were observed for this mixture in THF. The irreversible broad oxidation peak (E _p = 1.22 V (Fc^0/+)) was observed in CH₂Cl₂. The reversible reduction peak (E° = –3.16 V) and irreversible oxidation peak (E _p = 1.22 V) were attributed to the most stable hydrofullerene C₇₀H₃₆. The irreversible reduction (E _p = –3.37 V) and oxidation (E _p = 1.22 V) peaks were attributed to hydrofullerenes C₇₀H_44—46 with a higher degree of hydrogenation. The values of an electrochemical gap, which is an analog of the energy gap (HOMO—LUMO), are 4.38 and 4.59 V for C₇₀H₃₆ and C₇₀H_44—46, respectively, and indicate that these hydrofullerenes are sufficiently hard molecules with low reactivity in redox reactions.     

NiSe2 nanoparticles embedded in CNT networks: Scalable synthesis and superior electrocatalytic activity for the hydrogen evolution reaction

For the first time, NiSe₂ nanoparticles embedded in CNT networks have been synthesized via spray-drying followed by a selenization process. The NiSe₂/CNTs hybrid (NCH) delivers superior electrocatalytic performance for HER. It has a low onset potential of ~ 159 mV and a cathode current density of 35.6 mA cm^− 2 at − 250 mV vs RHE; more importantly, the Tafel slope has a very low value of 29 mV dec^− 1, which is comparable to a platinum (Pt) catalyst; in addition, it is stable even after 1000 cycles. The superior HER performance of NCH is attributed to its unique structure, which is composed of ultrathin NiSe₂ nanoparticles homogenously embedded in highly conductive and porous CNT networks. This not only provides abundant HER active sites, but also guarantees robust contact between the NiSe₂ nanoparticles and the CNT networks. The present study provides new insights into the large-scale and low-cost synthesis of a highly effective and stable NiSe₂-based electrocatalyst which could be extended to large-scale production of other non-precious metal hybrid catalysts with low cost, high efficiency and excellent stability.     

Fabrication and electrochemical performance of nickel ferrite nanoparticles as anode material in lithium ion batteries

Nano-sized nickel ferrite (NiFe₂O₄) was prepared by hydrothermal method at low temperature. The crystalline phase, morphology and specific surface area (BET) of the resultant samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and nitrogen physical adsorption, respectively. The particle sizes of the resulting NiFe₂O₄ samples were in the range of 5–15 nm. The electrochemical performance of NiFe₂O₄ nanoparticles as the anodic material in lithium ion batteries was tested. It was found that the first discharge capacity of the anode made from NiFe₂O₄ nanoparticles could reach a very high value of 1314 mAh g⁻¹, while the discharge capacity decreased to 790.8 mAh g⁻¹ and 709.0 mAh g⁻¹ at a current density of 0.2 mA cm⁻² after 2 and 3 cycles, respectively. The BET surface area is up to 111.4 m² g⁻¹. The reaction mechanism between lithium and nickel ferrite was also discussed based on the results of cycle voltammetry (CV) experiments.     

High-performance thin-film Li4Ti5O12 electrodes fabricated by using ink-jet printing technique and their electrochemical properties

Li₄Ti₅O₁₂ thin-film anode with high discharge capacity and excellent cycle stability for rechargeable lithium ion batteries was prepared successfully by using ink-jet printing technique. The prepared Li₄Ti₅O₁₂ thin film were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammograms, and galvanostatic charge–discharge measurements. It was found that the average thickness of 10-layer Li₄Ti₅O₁₂ film was about 1.7~1.8 μm and the active material Li₄Ti₅O₁₂ in the thin film was nano-sized about 50–300 nm. It was also found that the prepared Li₄Ti₅O₁₂ thin film exhibited a high discharge capacity of about 174 mAh/g and the discharge capacity in the 300th cycle retained 88% of the largest discharge capacity at a current density of 10.4 μA/cm² in the potential range of 1.0–2.0 V.     

InP as new anode material for lithium ion batteries

InP thin film has been successfully fabricated by pulsed laser deposition (PLD) and was investigated for its electrochemistry with lithium for the first time. InP thin film presented a large reversible discharge capacity around 620 mAh g^?1. The reversibility of the crystalline structure and electrochemical reaction of InP with lithium were revealed by using ex situ XRD and XPS measurements. The high reversible capacity and stable cycle of InP thin film electrode with low overpotential made it one of the promise energy storage materials for future rechargeable lithium batteries.     

Tremella-like molybdenum dioxide consisting of nanosheets as an anode material for lithium ion battery

Tremella-like structured MoO₂ consisting of nanosheets was obtained via a Fe₂O₃-assisted hydrothermal reduction of MoO₃ in ethylenediamine aqueous solution. The as-prepared product was characterized and tested with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and capacity measurement as anode material for lithium ion batteries. This structured MoO₂ shows very high reversible capacity (>600 mA h g⁻¹), good rate capability and cycling performance, presenting potential application as anode material for lithium ion batteries with high rate capability and high capacity.