Thermal simulation of large-scale lithium secondary batteries using a graphite–coke hybrid carbon negative electrode and LiNi0.7Co0.3O2 positive electrode

Thermal simulation was applied to 2 Wh-class cells (diameter 14.2 mm, height 50 mm) using LiNi_0.7Co_0.3O₂ or LiCoO₂ as the positive electrode material, in order to clarify the thermal behavior of the cells during charge and discharge. The thermal simulation results for the 2 Wh-class cells showed a good agreement with measured temperature values. The heat generation of a cell using LiNi_0.7Co_0.3O₂ was found to be much less than that using LiCoO₂ during discharge. This difference was considered to be caused by the difference in the change of entropy. A 250 Wh-class cell (diameter 64 mm, height 296 mm) was also constructed using LiNi_0.7Co_0.3O₂ and thermal simulation was applied. We confirmed that the results of the thermal simulation agreed with measured values and that this simulation model is effective for analyzing the thermal behavior of large-scale lithium secondary batteries.     

Novel electrospun poly(vinylidene fluoride-co-hexafluoropropylene)–in situ SiO2 composite membrane-based polymer electrolyte for lithium batteries

Composite membranes of poly(vinylidene fluoride-co-hexafluoropropylene) {P(VdF-HFP)} and different composition of silica have been prepared by electrospinning polymer solution containing in situ generated silica. These membranes are made up of fibers of 1–2 μm diameters. These fibers are stacked in layers to produce fully interconnected pores that results in high porosity. Polymer electrolytes were prepared by immobilizing 1 M LiPF₆ in ethylene carbonate (EC)/dimethyl carbonate (DMC) in the membranes. The composite membranes exhibit a high electrolyte uptake of 550–600%. The optimum electrochemical properties have been observed for the polymer electrolyte containing 6% in situ silica to show ionic conductivity of 8.06 mS cm⁻¹ at 20 °C, electrolyte retention ratio of 0.85, anodic stability up to 4.6 V versus Li/Li⁺, and a good compatibility with lithium metal resulting in low interfacial resistance. A first cycle specific capacity of 170 mAh g⁻¹ was obtained when the polymer electrolyte was evaluated in a Li/lithium iron phosphate (LiFePO₄) cell at 0.1 C-rate at 25 °C, corresponding to 100% utilization of the cathode material. The properties of composite membrane prepared with in situ silica were observed to be comparatively better than the one prepared by direct addition of silica.     

Synergic effect of V2O5 and P2O5 on the sealing properties of barium–strontium–alumino-silicate glass/glass–ceramics

The effect of combined addition of P₂O₅ and V2O₅ on structural and sealing properties of glasses with nominal composition (mol.%) 27SiO₂–23SrO–32BaO–4Al₂O₃–10B₂O₃–(4-x)P₂O₅–xV₂O₅ is reported in the present study. ²⁹Si,³¹P,⁵¹V,²⁷Al and ¹¹B MAS-NMR have been used to characterize the local environment in the glasses and glass–ceramics. The main network-forming elements (Si, Al, B) are not significantly affected, however, P and V show different local environment when they are associated in the composition. Characteristic temperatures (T_g, T_soft, T_shrink) decrease when V₂O₅ is added to the glass composition, which enable to decrease the sealing temperature. However, the combined addition of P₂O₅ and V₂O₅ is favorable to avoid extensive crystallization during sealing operation. TEC of the glass and glass–ceramics samples is found compatible with those of metallic alloys and do not change after heat treatment. EPMA images show that the seals have good thermal and chemical stabilities when treated up to 1500 h at 800 °C. Sandwich seals tested under pressure are resistant to thermal cycling.     

Enhancement of the high-temperature performance of advanced nickel–metal hydride batteries with NaOH electrolyte containing NaBO2

In this paper, an alternative approach to improve the high-temperature performance of nickel–metal hydride (Ni–MH) batteries is proposed by introducing NaOH electrolyte with sodium metaborate (NaBO₂) additives. Compared with conventional batteries using KOH electrolyte, the in-house prepared batteries with proposed electrolytes exhibit an enhanced discharge capacity, improved high-rate discharge ability, increased cycle stability and reduced self-discharge rate at an elevated temperature (70 °C). The charge acceptance of these Ni–MH batteries at 70 °C is over 96% at a charge/discharge rate of 1 C. These performance improvements are ascribed to the increased oxygen evolution overpotential, slower oxygen evolution rate and lower electrochemical impedance, as indicated by CV, steady-state polarization measurements and EIS. The results suggest that the proposed approach be an effective way to improve the high-temperature performance of Ni–MH batteries.     

Solvothermal synthesis ZnS–In2S3–Ag2S solid solution coupled with TiO2−xSx nanotubes film for photocatalytic hydrogen production

ZnS–In₂S₃–Ag₂S solid solution coupled with TiO_2-xS_x nanotubes film catalyst has been successfully prepared by a two-step process of anodization and solvothermal methods for the first time. The as-prepared photo-catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–Visible diffuse reflectance spectra (UV–Vis DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. The results show that the ZnS–In₂S₃–Ag₂S solid solution are deposited on the surface of TiO₂NTs nanotubes under the solvothermal conditions, by which S atoms are incorporated into the lattice of TiO₂ through substituting the sites of oxygen atoms. Such ZnS–In₂S₃–Ag₂S@TiO_2-xS_x nanotubes composite presents the enhanced absorption in visible region and the efficient transfer of photoelectron between the solid solution and TiO_2-xS_x nanotubes, which determines the excellent photocatalytic activity for the photocatalytic hydrogen evolution from aqueous solutions containing the sacrificial reagents of Na₂S and Na₂SO₃ under 500 W Xe lamp irradiation.     

Three-dimensional Li2O–NiO–CoO composite thin-film anode with network structure for lithium-ion batteries

Three-dimensional Li₂O–NiO–CoO composite thin-film electrodes deposited on stainless steel substrates were synthesized by the electrostatic spray deposition (ESD) technique at 240 and 295 °C. The morphology of the composite was investigated by scanning electron microscopy. X-ray diffraction indicated that the as-deposited films are composites of Li₂O, NiO and CoO. The effects of the solvent used to dissolve the starting materials on the morphology and electrochemical performance of the thin-film electrodes were also investigated. It was found that the as-deposited thin-film electrodes exhibited a high reversible capacity (>800 mAh g⁻¹ when cycled between 0.01 and 3 V at a cycling rate of 0.5 C), good capacity retention, and outstanding rate capability. The superior electrochemical performance may have resulted from the combination of the very porous structure and the three-dimensional network of the as-deposited thin-film electrodes, which contributed to a high surface area, favoured lithium-ion diffusion, and formed a stable integral structure. The thin-film electrodes could be promising anodes for use in high power and high energy density lithium-ion batteries.     

Homogeneous core–shell NiCo2S4 nanorods as flexible electrode for overall water splitting

Exploring low-cost and highly efficient Water splitting electrocatalyst has been recognized as one of the most challenging and promising ways. NiCo₂S₄ core-shell nanorods supported on nickel foam (NF) have been fabricated by a facile hydrothermal method. The electrochemical performance of NiCo₂S₄@NiCo₂S₄ for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is studied. NiCo₂S₄@NiCo₂S₄/NF exhibits a significantly improved OER and HER performance with an overpotential of 200 mV at 40 mA/cm² and an overpotential of 190 mV at 10 mA/cm². The combination of low charge-transfer resistance, enhanced interaction and charge transport as well as large electrochemical double-layer capacitance enables superior OER and HER. The NiCo₂S₄@NiCo₂S₄/NF nanorod electrode shows excellent electrocatalytic activity with a low voltage 1.57 V and stability with long hour electrolysis, which is highly satisfactory for a prospective bifunctional electrocatalyst.     

Production of H2 and C2 hydrocarbons from methane in a proton conducting solid electrolyte cell using a Au–5Ce–5Na2WO4/SiO2 anode

A novel approach of upgrading methane towards the simultaneous production/separation of H₂ and C₂ hydrocarbons (ethane and ethylene), is developed. The reaction system was studied in a solid state proton (H⁺) conducting cell. Mixtures of methane, steam (and oxygen) were introduced over the anode, while an inert gas flowed over the cathode. Under open-circuit, the reacting mixture produced H₂, C₂H₆, C₂H₄, CO and CO₂. Under closed-circuit and when protons (H⁺) were electrochemically “pumped” from the anode to the cathode, a considerable increase in the production of H₂ was observed while the production of C₂ compounds remained essentially unaffected.     

Effects of the addition of ZnO and Y2O3 on the electrochemical characteristics of a Ni(OH)2 electrode in nickel–metal hydride secondary batteries

This study examined the effects of the addition of ZnO and Y₂O₃ on the electrochemical characteristics of a Ni(OH)₂ electrode in nickel–metal hydride (Ni–MH) secondary batteries. The discharge capacity of the electrode was less affected by the addition of ZnO and Y₂O₃ at a 0.2 C-rate and 25 °C. However, the addition of Y₂O₃ deteriorated the discharge capacity and the cycle life of the electrode by increasing the charge transfer resistance of the electrode at an increased C-rate of 1 C and 25 °C. Under severer conditions at 1 C-rate and 60 °C, the electrode materials were separated from the current collector and, accordingly, the discharge capacity was abruptly degraded with cycling for the electrodes comprising only 4 wt% ZnO or 4 wt% Y₂O₃. In contrast, the electrodes containing both 2 wt% ZnO and 2 wt% Y₂O₃ exhibited stable discharge capacity with cycling and excellent cycle life due to the high overvoltage for oxygen evolution. The present results indicate that the addition of ZnO and Y₂O₃ with an optimum composition suppresses oxygen evolution in the interfaces between active materials and the current collector and improves the cycle life of the electrode.     

Mechanochemical synthesis of α-Fe2O3 nanoparticles and their application to all-solid-state lithium batteries

α-Fe₂O₃ fine particles have been prepared by a mechanochemical process and a solution process. α-Fe₂O₃ nanoparticles with aggregates composed of the several tens nm primary particles were produced by the mechanochemical process. The nanoparticles were applied to the electrode as an active material for all-solid-state lithium batteries and the electrochemical properties of the cell were investigated. Typical charge–discharge curves, as seen in the liquid type cell using the α-Fe₂O₃ nanoparticles as an electrode were observed in the all-solid-state cell. The first discharge capacity of the cell of about 780 mAh g⁻¹ was, however, smaller than the capacity of a cell using α-Fe₂O₃ particles prepared by the solution process, which were monodispersed particles of 250 nm without aggregates. In order to develop electrochemical performance of all-solid-state batteries, it is important to use the electrode particles without aggregation which lead to the formation of good solid–solid interface between active material and solid electrolyte particles.C     

Hydrothermal synthesis of mixed crystal phases TiO2–reduced graphene oxide nanocomposites with small particle size for lithium ion batteries

A rutile and anatase mixed crystal phase of nano-rod TiO₂ and TiO₂–reduced graphene oxide (TiO₂–RGO) nanocomposites with small particle size were prepared via a facile hydrothermal approach with titanium tetrabutoxide and graphene oxide as the precursor. Hydrolysis of titanium tetrabutoxide and mild reduction of graphene oxide were simultaneously carried out. Compared with traditional multistep methods, a novel green synthetic route to produce TiO₂–RGO without toxic solvents or reducing agents was employed. TiO₂–RGO as anode of lithium ion batteries was characterized by extensive measurements. The nanocomposites exhibited notable improvement in lithium ion insertion/extraction behavior compared with TiO₂, indicating an initial irreversible capacity and a reversible capacity of 295.4 and 112.3 mA h g⁻¹ for TiO₂–RGO after 100 cycles at a high charge rate of 10 C. The enhanced electrochemical performance is attributed to increased conductivity in presence of reduced graphene oxide in TiO₂–RGO, a rutile and anatase mixed crystal phase of nano-rod TiO₂/GNS composites, small size of TiO₂ particles in nanocomposites, and enlarged electrode–electrolyte contact area, leading to more electroactive sites in TiO₂–RGO.     

Synthesis and electrochemistry of cubic rocksalt Li–Ni–Ti–O compounds in the phase diagram of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2

On the basis of extreme similarity between the triangle phase diagrams of LiNiO₂–LiTiO₂–Li[Li_1/3Ti_2/3]O₂ and LiNiO₂–LiMnO₂–Li[Li_1/3Mn_2/3]O₂, new Li–Ni–Ti–O series with a nominal composition of Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ (0 ≤ z ≤ 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li–Ni–Ti–O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi_1/2Ti_1/2O₂ and Li[Li_1/3Ti_2/3]O₂ (high temperature form). Charge–discharge tests showed that Li–Ni–Ti–O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g⁻¹ for 0.2 ≤ z ≤ 0.27) at room temperature in the voltage range of 4.5–2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g⁻¹ for 0 ≤ z ≤ 0.27), cycleability and rate capability at an elevated temperature of 50 °C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li⁺. A preliminary electrochemical comparison between Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ (0 ≤ z ≤ 0.5) and Li_6/5Ni_2/5Ti_2/5O₂ indicated that charge–discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ while +3 in Li_6/5Ni_2/5Ti_2/5O₂. Reduction of Ti⁴⁺ at a plateau of around 2.3 V could be clearly detected in Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ with 0.27 ≤ z ≤ 0.5 at 50 °C after a deep charge associated with charge compensation from oxygen ion during initial cycle.     

Hydrogen storage properties of destabilized MgH2–Li3AlH6 system

To improve the dehydrogenation properties of MgH₂, a novel hydrogen storage system, MgH₂–Li₃AlH₆, is prepared by mechanochemical milling. Three physical mixtures containing different mole ratios (1:4, 1:1 and 4:1) of MgH₂ and Li₃AlH₆ are studied and there exists a mutual destabilization effect between the components. The last mixture shows a capacity of 6.5 wt% H₂ with the lowest starting temperature of dehydrogenation (170 °C). First, Li₃AlH₆ decomposes into Al, LiH and H₂, and then the as-formed Al can easily destabilize MgH₂ to form the intermetallic compound Mg₁₇Al₁₂ at a temperature of 235 °C, which is about 180 °C lower than the decomposition temperature of pristine MgH₂. Finally, the residual MgH₂ undergoes a self-decomposition whose apparent activation energy has been reduced by about 22 kJ mol⁻¹ compared with pristine MgH₂. At a constant temperature of 250 °C, the mixture can dehydrogenate completely under an initial vacuum and rehydrogenate to form MgH₂ under 2 MPa H₂, showing good cycle stability after the first cycle with a capacity of 4.5 wt% H₂. The comparison between 4 MgH₂ + Li₃AlH₆ and 4 MgH₂ + LiAlH₄ mixtures is also investigated.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

Charge transfer behaviors over MOF-5@g-C3N4 with NixMo1−xS2 modification

The composite photocatalyst Ni_xMo_1?xS₂/MOF-5@g-C₃N₄ was successfully synthesized by means of hydrothermal with two step methods and the effective photocatalytic activity improvement was obtained. With the introduction of Ni_xMo_1?xS₂, the H₂ production reached the maximum about 319 μmol under continuous visible light irradiation for 5 h, which was 30 times higher than that of pure g-C₃N₄ photocatalyst. A series of characterization results shown that the MOF-5@g-C₃N₄ on the surface of Ni_xMo_1?xS₂ provided the more active sites and improved the efficiency of photo-generated charge separation with SEM, XRD, TEM, EDX, XPS, UV–vis DRS, BET, FTIR, transient fluorescence and electro-chemistry etc. and the results of which were in good mutual corresponding with each other. Furthermore, the reaction mechanism over the compound catalyst Ni_x-Mo_1?xS₂/MOF-5@g-C₃N₄ was proposed.     

Proton conductivities and structures of BaO–ZnO–P2O5 glasses in the ultraphosphate region for intermediate temperature fuel cells

Phosphate glasses are promising materials for electrolytes of intermediate temperature fuel cells, because they have good proton conductivity at 150–250 °C. However, the effects of the glass composition and melting condition on proton conductivities are unclear yet. In this work, the structures of BaO–ZnO–P₂O₅ glasses were investigated by magic angle spinning-nuclear magnetic resonance (MAS-NMR) and Raman spectroscopy, and the proton conductivities were measured by an AC impedance method. The proton conductivity of 30 mol%ZnO-70 mol%P₂O₅ glass melted at 800 °C reached 1 × 10⁻³ S/cm at 250 °C for. The proton transportation number of the ZnO–P₂O₅ glass was almost unity, confirmed by a hydrogen concentration cell. The power density of 0.4 mW/cm² was obtained for a fuel cell using the ZnO–P₂O₅ glass electrolyte at 250 °C. A branching phosphate structure was transformed into a middle phosphate structure by substituting BaO with ZnO, which caused an improvement in proton mobility.     

Adiabatic burning velocity of H2–O2 mixtures diluted with CO2/N2/Ar

Global warming due to CO₂ emissions has led to the projection of hydrogen as an important fuel for future. A lot of research has been going on to design combustion appliances for hydrogen as fuel. This has necessitated fundamental research on combustion characteristics of hydrogen fuel. In this work, a combination of experiments and computational simulations was employed to study the effects of diluents (CO₂, N₂, and Ar) on the laminar burning velocity of premixed hydrogen/oxygen flames using the heat flux method. The experiments were conducted to measure laminar burning velocity for a range of equivalence ratios at atmospheric pressure and temperature (300 K) with reactant mixtures containing varying concentrations of CO₂, N₂, and Ar as diluents. Measured burning velocities were compared with computed results obtained from one-dimensional laminar premixed flame code PREMIX with detailed chemical kinetics and good agreement was obtained. The effectiveness of diluents in reduction of laminar burning velocity for a given diluent concentration is in the increasing order of argon, nitrogen, carbon dioxide. This may be due to increased capabilities either to quench the reaction zone by increased specific heat or due to reduced transport rates. The lean and stoichiometric H₂/O₂/CO₂ flames with 65% CO₂ dilution exhibited cellular flame structures. Detailed three-dimensional simulation was performed to understand lean H₂/O₂/CO₂ cellular flame structure and cell count from computed flame matched well with the experimental cellular flame.     

Combustion,performance and emissions of a diesel engine with H2, CH4 and H2–CH4 addition

Experiments were conducted to investigate the combustion and emission characteristics of a diesel engine with addition of hydrogen or methane for dual-fuel operation, and mixtures of hydrogen–methane for tri-fuel operation. The in-cylinder pressure and heat release rate change slightly at low to medium loads but increase dramatically at high load owing to the high combustion temperature and high quantity of pilot diesel fuel which contribute to better combustion of the gaseous fuels. The performance of the engine with tri-fuel operation at 30% load improves with the increase of hydrogen fraction in methane and is always higher than that with dual-fuel operations. Compared with ULSD–CH₄ operation, hydrogen addition in methane contributes to a reduction of CO/CO₂/HC emissions without penalty on NO_x emission. Dual-fuel and tri-fuel operations suppress particle emission to the similar extent. All the gaseous fuels reduce the geometry mean diameter and total number concentration of diesel particulate. Tri-fuel operation with 30% hydrogen addition in methane is observed to be the best fuel in reducing particulate and NO_x emissions at 70 and 90% loads.