Electrochemical and electrical properties of Nb- and/or C-containing LiFePO4 composites

A study of LiFePO₄-based electrodes prepared through various synthesis conditions is presented. From X-Ray diffraction, high resolution transmission electron microscopy, electrochemical Li⁺ extraction/insertion and electrical conductivity data we conclude that the use of starting precursors such as Li₂CO₃, FeC₂O₄·2H₂O and/or Nb(OC₆H₅)₅ produces LiFePO₄-based composites containing significant amounts of carbon. We never succeeded in doping LiFePO₄ with Nb to yield Li_1−xNb_xFePO₄ but produced, instead, crystalline β-NbOPO₄ and/or an amorphous (Nb, Fe, C, O, P) “cobweb” around LiFePO₄ particles which is responsible for superior electrochemical activity. AC-conductivity measurements conclude to a total electrical conductivity of ∼10^− 9 S cm^− 1 at 25 °C with an activation energy of ca. 0.65 eV for pure LiFePO₄ and LiFePO₄/β-NbOPO₄ composites. C-containing LiFePO₄ samples, including those that were tentatively but unsuccessfully doped with Nb, are much more conductive (up to 1.6 · 10^− 1 S cm^− 1) with an activation energy ΔE∼0.08 eV.     

Synthesis of LiFePO4 nanoparticles and their electrochemical properties

LiFePO₄ nanoparticles were synthesized via polyol process. The temperature of the solution was rapidly increased up to 320 °C to obtain larger particles and the temperature was maintained for 16 h in a round-bottomed flask attached to a refluxing condenser. The X-ray diffractrion (XRD), pattern was indexed on the basis of orthorhombic olivine structure. The LiFePO₄ compound prepared through polyol process exhibited a high crystallinity. The particles show the various shapes with size ranging from 100 to 300 nm. The initial discharge curve of LiFePO₄ capacity shows 168 mA h/g at the 0.1C rate in the voltage range of 2.5–4 V with well-formed plateau.     

A new insight into the LiFePO4 delithiation process

Raman and Fourier transform infrared measurements for Li_xM_0.03Fe_0.97PO₄, M = Cr, Cu, Al, Ti were performed. The spectra for delithiated samples to a low content of lithium extraction are practically the same as those of LiFePO₄. For a high content of lithium extraction, the spectra repeat that of FePO₄. In the case of the Li_0.11FePO₄ oxide the spectra cannot be reproduced just by the superposition of the end member profiles. An additional broad band contribution is found in both Raman and infrared spectra probably due to a disordered structure present in the mixture. This suggests that the well accepted two-phase model for the delithiation process in LiFePO₄ is incorrect. The model should be revised to include the new phase as detected here for a particular level of lithium extraction close to that of complete oxidation of the Fe²⁺ ions to Fe³⁺.     

SnO2-decorated multiwalled carbon nanotubes and Vulcan carbon through a sonochemical approach for supercapacitor applications

Multiwalled carbon nanotubes (MWCNTs) and Vulcan carbon (VC) decorated with SnO₂ nanoparticles were synthesized using a facile and versatile sonochemical procedure. The as-prepared nanocomposites were characterized by means of transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infra red spectroscopy. It was evidenced that SnO₂ nanoparticles were uniformly distributed on both carbon surfaces, tightly decorating the MWCNTs and VC. The electrochemical performance of the nanocomposites was evaluated by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂/MWCNTs nanocomposites show a higher capacity than the SnO₂/VC nanocomposites. Concretely, the SnO₂/MWCNTs electrodes exhibit a specific capacitance of 133.33 F g⁻¹, whereas SnO₂/VC electrodes exhibit a specific capacitance of 112.14 F g⁻¹ measured at 0.5 mA cm⁻² in 1 M Na₂SO₄.     

Controllable synthesis of rice-shape Alq3 nanoparticles with single crystal structure

We report the controllable growth of rice-shape nanoparticles of Alq₃ by an extremely facile self-assembly approach. Possible mechanisms have been proposed to interpret the formation and controlled process of the single crystal nanoparticles. The field-emission performances (turn-on field 7 V μm⁻¹, maximum current density 2.9 mA cm⁻²) indicate the potential application on miniaturized nano-optoelectronics devices of Alq₃-based. This facile method can potentially be used for the controlled synthesis of other functional complexes and organic nanostructures.     

Cellulose-based carbon—A potential anode material for lithium-ion battery

A series of hard carbons was produced by the carbonization of microcrystalline cellulose powder in the temperature range of 950–1100 °C. The properties of the carbons were characterized using elemental analysis, X-ray diffraction and N₂ and CO₂ adsorption. The effect of heat-treatment temperature (HTT), pyrolytic carbon (PC) coating and discharging mode on the lithium insertion/deinsertion behavior of the carbons was assessed in a coin-type half-cell with metal lithium cathode. Increasing cellulose HTT modifies mostly carbon porosity, the surface area (S_DFT) decreases from about 500 to 167 m² g⁻¹. It is associated with lowering the reversible C_rev and irreversible C_irr capacities, but without improving relatively low (0.72) 1st cycle coulombic efficiency. Applying constant current (CC)+constant voltage (CV) discharging mode instead of conventional CC enhances the reversible capacity by 15–18%. PC coating is effective in reducing C_irr by ∼20% with a little change of C_rev. The best capacity parameters, C_rev of 458 mA h g⁻¹ and C_irr of 139 mA h g⁻¹, were measured for PC coated 1000 °C carbon. The prolonged cycling of full-cell assembled with anode of the carbon and commercial cathode revealed that after initial 20 cycles the capacity decay (0.029 mA h/cycle) is comparable to that of commercial cell with graphite-based anode.     

The synthesis and properties of nanocrystalline electrode materials by mechanical alloying

In this work, we have experimentally studied the structure and electrochemical properties of nanocrystalline TiFe- and LaNi₅-type alloys. These materials were prepared by mechanical alloying (MA) followed by annealing. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. It was found that the respective replacement of Fe in TiFe by Ni and/or by Cr, Co, Mo, Zr improved not only the discharge capacity but also the cycle life of these electrodes. In the nanocrystalline TiFe_0.25Ni_0.75, powder discharge capacity up to 155 mA h g⁻¹ was measured (at 40 mA g⁻¹ discharge current). On the other hand, a partial substitution of Ni by Al or Mn in LaNi_5−xM_x alloy leads to an increase in discharge capacity. The alloying elements such as Al, Mn and Co greatly improved the cycle life of LaNi₅ material. For example, in the nanocrystalline LaNi_3.75Mn_0.75Al_0.25Co_0.25 powder, discharge capacity up to 258 mA h g⁻¹ was measured (at 40 mA g⁻¹ discharge current). The studies show, that electrochemical properties of Ni–MH batteries are the function of the microstructure and the chemical composition of used electrode materials.     

Sonochemically synthesized MnO2 nanoparticles as electrode material for supercapacitors

In this study, manganese oxide (MnO₂) nanoparticles were synthesized by sonochemical reduction of KMnO₄ using polyethylene glycol (PEG) as a reducing agent as well as structure directing agent under room temperature in short duration of time and characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscope (SEM), Transmission electron microscopy (TEM) and Brunauer–Emmett–Teller (BET) analysis. A supercapacitor device constructed using the ultrasonically-synthesized MnO₂ nanoparticles showed maximum specific capacitance (SC) of 282 Fg⁻¹ in the presence of 1 M Ca(NO₃)₂ as an electrolyte at a current density of 0.5 mA cm⁻² in the potential range from 0.0 to 1.0 V and about 78% of specific capacitance was retained even after 1000 cycles indicating its high electrochemical stability.     

Molybdenum carbide nano-sheet as a high capacity anode material for monovalent alkali metal-ion batteries—Theoretical investigation

This contribution presents a theoretical investigation of monovalent metal-ion adsorption and diffusion on two-dimensional (2D) buckled nanostructure of molybdenum carbide (MoC) by using the first principle method. We find that buckled MoC nanostructure exhibits great stability, semiconducting electronic property, and high performance as electrode material. Interestingly, Crystal Orbital Hamilton population (COHP) method results show that buckled MoC is chemically stable in a wide range of temperatures, and various Li, Na, ions adsorbed configurations, which is beneficial for anode materials. Especially, single-layer MoC exhibits a superior theoretical capacity of 993.16 mA h g⁻¹ for Li-ions and 496.58 mA h g⁻¹ for Na/K-ions. The storage capacity of 1200 mA h g⁻¹ is found for the adsorption of ions on multilayer bulk MoC. Moreover, migration energy barriers are predicted as 0.38 eV for Li, 0.32 eV for Na, and 0.24 eV for K; these remarkable results determine the applicability of buckled MoC as ideal anode material for metal-ion battery applications.     

Rechargeability improvement of δ-type chemical manganese dioxide with the co-doping of Bi and Ni in alkaline electrolyte

δ-MnO₂ with the doping of Ni and Bi was prepared through a simple chemical precipitation/oxidation method. Its structure was confirmed by the X-ray diffraction tests. The results of cyclic voltammetry and galvanostatic charge–discharge tests showed that both the doping of Bi and Ni benefited the electrochemical activity of the MnO₂ electrode. Compared to the un-doped electrode, the Bi-doped one showed larger discharge capacity and the Ni-doped one showed higher discharge potential and better cycleability. With the co-doping of 5 wt% Bi and 10 wt% Ni, the discharge capacity of the MnO₂ electrode reached 252 mA h g^?1 at a 0.2C rate and 116 mA h g^?1 at a 1C rate, respectively. Its capacity remained in 105 mA h g^?1 after 50 cycles at a 1C rate, but the capacity of a commercial electrolytic MnO₂ electrode was only 37 mA h g^?1.     

Electrically forced microthreading of highly viscous dielectric liquids

The behaviour of three high viscosity (4875, 12 125 and 58 560 mPa s), dielectric liquids was investigated at flow rates of 10⁻¹⁰, 10⁻¹² and 10⁻¹⁴ m³ s⁻¹ and the applied voltage range 6–15 kV. In these experiments, due to the low electrical conductivity of the liquids (10⁻¹³ S m⁻¹) and therefore the ensuing high electrical relaxation time, classical electrohydrodynamic atomization conditions are not satisfied. Only dripping and unstable jetting were observed at 4875 mPa s. A transition from no jetting to stable microthreading was observed for the 12 125 and 58 560 mPa s samples. The relics accompanying the transition were found to change from discrete droplets to a continuous filament. Stable microthreading, which generates uniform filaments, was obtained for the 12 125 mPa s sample at flow rates 10⁻¹⁰ and 10⁻¹² m³ s⁻¹ and in the case of the 58 560 mPa s sample at all the flow rates investigated. The high viscosity assisted stable microthreading with the filament diameter decreasing with increasing applied voltage and more dramatically decreasing with reducing flow rate.     

Rapid synthesis of LiFePO4/C composite by microwave method

A highly crystalline LiFePO₄/C phase was successfully synthesized by a microwave irradiation method in 4 min. SEM and particle size analysis indicate that the particle size of resulting LiFePO₄/C is much smaller than that of the solid-state derived sample and that it mostly distributes in the range of 160–600 nm. Cycling tests show that the sample prepared by microwave method can deliver 150 mAh g^? 1 at 17 mA g^? 1(0.1C). Further AC impedance measurements reveal that the LiFePO₄ electrode can be well activated after the first cycle as reflected by the dramatic decrease in the charge transfer resistance.     

Sonochemical synthesis of LiNi0.5Mn1.5O4 and its electrochemical performance as a cathode material for 5 V Li-ion batteries

LiNi_0.5Mn_1.5O₄ was synthesized as a cathode material for Li-ion batteries by a sonochemical reaction followed by annealing, and was characterized by XRD, SEM, HRTEM and Raman spectroscopy in conjunction with electrochemical measurements. Two samples were prepared by a sonochemical process, one without using glucose (sample-S1) and another with glucose (sample-S2). An initial discharge specific capacity of 130 mA h g⁻¹ is obtained for LiNi_0.5Mn_1.5O₄ at a relatively slow rate of C/10 in galvanostatic charge–discharge cycling. The capacity retention upon 50 cycles at this rate was around 95.4% and 98.9% for sample-S1 and sample-S2, respectively, at 30 °C.     

Optimization of simultaneous ultrasound assisted toxic dyes adsorption conditions from single and multi-components using central composite design: Application of derivative spectrophotometry and evaluation of the kinetics and isotherms

Present study is devoted on the efficient application of Sn (O, S)-NPs -AC for simultaneous sonicated accelerated adsorption of some dyes from single and multi-components systems. Sn (O, S) nanoparticles characterization by FESEM, EDX, EDX mapping and XRD revel its nano size structure with high purity of good crystallinity. Present adsorbent due to its nano spherical shape particles with approximate diameter of 40–60 nm seems to be highly effective in this regard. The effects of five variables viz. pH (3.5–9.5), 0.010–0.028 g of adsorbent and 0.5–6.5 min mixing by sonication is good and practical conditions for well and expected adsorption of MB and CV over concentration range of 3–15 mg L⁻¹. Combination of response surface methodology (RSM) based on central composite design (CCD) and subsequent of analysis of variance (ANOVA) and t-test statistics were used to test the significance of the independent variables and their interactions. Regression analysis reveal that experimental data with high repeatability and efficiency well represented by second-order polynomial model with coefficient of determination value of 0.9988 and 0.9976 for MB and CV, respectively following conditions like pH 8.0, 0.016 g adsorbent, 15 mg L⁻¹ of both dyes 4 min sonication time is proportional with achievement of experimental removal percentage of 99.80% of MB and 99.87% of CV in batch experiment. Evaluation and estimation of adsorption data with Langmuir and Freundlich isotherm well justify the results based on their correlation coefficient and error analysis confirm that Langmuir model is good model with adsorption capacity of 109.17 and 115.34 mg g⁻¹ in single system and 95.69 and 102.99 mg g⁻¹ in binary system for MB and CV, respectively. MB and CV kinetic and rate of adsorption well fitted by pseudo-second order equation both in single and binary systems and experimental results denote more and favorable adsorption of CV than respective value in single system. The pseudo-second-order rate constant k₂ in binary system larger than single system.     

Diffusional mechanism of deintercalation in LiFe1 − yMnyPO4 cathode material

The paper presents the investigations on the structural, electrical and electrochemical properties of Mn substituted phospho-olivines LiFe_1 − yMn_yPO₄ and of W, Ti or Al doped LiFePO₄. The microscopic nature of the observed macroscopic, metallic-like conductivity of W, Ti, Al doped phospho-olivine samples is discussed. Some fundamental arguments against the bulk type conductivity are presented.A single phase, diffusional mechanism of deintercalation was found to appear for Mn-substituted LiFe_1 − yMn_yPO₄ samples in the whole range of lithium concentration, in contrast to the pure LiFePO₄, LiMnPO₄ and W, Ti, Al doped phospho-olivines, where a two-phase mechanism of electrochemical lithium extraction/insertion is observed.     

Transport and phase dynamics of poly(vinyl pyrrolidone) doped plastically crystalline N-methyl-N-propylpyrrolidinium tetrafluoroborate

The plastic crystal phase forming N-methyl-N-propylpyrrolidinium tetrafluoroborate organic salt (P₁₃BF₄) was combined with 2, 5 and 10 wt.% poly(vinyl pyrrolidone) (PVP). The ternary 2 wt.% PVP/2 wt.% LiBF₄/P₁₃BF₄ was also investigated. Thermal analysis, conductivity, optical thermomicroscopy, and Nuclear Magnetic Resonance (¹¹B, ¹⁹F, ¹H, ⁷Li) were used to probe the fundamental transport processes. Both the onset of phase I and the final melting temperature were reduced with increasing additions of PVP. Conductivity in phase I was 2.6 × 10^− 4 S cm^− 1 5.2 × 10^− 4 S cm^− 1 1.1 × 10^− 4 S cm^− 1 and 3.9 × 10^− 5 S cm^− 1 for 0, 2, 5 and 10 wt.%PVP/P₁₃BF₄, respectively. Doping with 2 wt.% LiBF₄ increased the conductivity by up to an order of magnitude in phase II. Further additions of 2 wt.% PVP slightly reduced the conductivity, although it remained higher than for pure P₁₃BF₄.     

Synthesis of TiO2/WO3 nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination

Through an ultrasound assisted method, TiO₂/WO₃ nanoparticles were synthesized at room temperature. The XRD pattern of as-prepared TiO₂/WO₃ nanoparticles matches well with that of pure monoclinic WO₃ and rutile TiO₂ nanoparticles. TEM images show that the prepared TiO₂/WO₃ nanoparticles consist of mixed square and hexagonal shape particles about 8–12 nm in diameter. The photocatalytic activity of TiO₂/WO₃ nanoparticles was tested for the degradation of a wastewater containing methylene blue (MB) under visible light illumination. The TiO₂/WO₃ nanoparticles exhibits a higher degradation rate constant (6.72 × 10⁻⁴ s⁻¹) than bare TiO₂ nanoparticles (1.72 × 10⁻⁴ s⁻¹) under similar experimental conditions.     

Synthesis of ammonia at atmospheric pressure with Ce0.8M0.2O2−δ (M = La,Y, Gd,Sm) and their proton conduction at intermediate temperature

Ionic conduction in fluorite-type structure oxide ceramics Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10^− 9, 7.5 × 10^− 9, 7.7 × 10^− 9, 8.2 × 10^− 9 mol s^− 1 cm^− 2, respectively.     

A Boubaker polynomials expansion scheme (BPES)-related protocol for measuring sprayed thin films thermal characteristics

Measurements of In₂S₃ and ZnIn₂S₄ sprayed thin films thermal characteristics have been carried out using the photodetection technique. The thermal conductivity k and diffusivity D were obtained using a new protocol based on photothermal signal parameters analysis. Measured values of k and D were respectively, (15.2 ± 0.85) W m⁻¹K⁻¹ and (69.8 ± 7.1) × 10⁻⁶ m²s⁻¹ for In₂S₃, (7.2 ± 0.7) W m⁻¹K⁻¹ and (32.7 ± 4.3) × 10⁻⁶ m²s⁻¹ for ZnIn₂S₄. These values are extremely important since similar compounds are more and more proposed as Cd-free alternative materials for solar cells buffer layers.     

Sonochemical synthesis,structural, magnetic and grain size dependent electrical properties of NdVO4 nanoparticles

NdVO₄ nanoparticles are successfully synthesized by efficient sonochemical method using two different structural directing agents like CTAB and P123. The phase formation and functional group analysis are carried out using X-ray diffraction (XRD) and fourier transform infra red (FT-IR) spectra, respectively. Using Scherrer equation the calculated grain sizes are 27 nm, 24 nm and 20 nm corresponding to NdVO₄ synthesized by without surfactant, with CTAB and P123, respectively. The TEM images revealed that the shape of NdVO₄ particles is rice-like and rod shaped particles while using CTAB and P123 as surfactants. The growth mechanism of NdVO₄ nanoparticles is elucidated with the aid of TEM analysis. From electrical analysis, the conductivity of NdVO₄ nanoparticles synthesized without surfactant showed a higher conductivity of 5.5703 × 10⁻⁶ S cm⁻¹. The conductivity of the material depends on grain size and increased with increase in grain size due to the grain size effect. The magnetic measurements indicated the paramagnetic behavior of NdVO₄ nanoparticles.