Synthesis of layered cathode materials Li[CoxNiyMn1−x−y]O2 from layered double hydroxide precursors

Cathode materials Li[Co_xNi_yMn_1?x?y]O₂ for lithium secondary batteries have been prepared by a new route using layered double hydroxides (LDHs) as a precursor. The resulting layered phase with the α-NaFeO₂ structure crystallizes in the rhombohedral system, with space group R-3m having an interlayer spacing close to 0.47 nm. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation states of Co, Ni and Mn. The effects of varying the Co/Ni/Mn ratio on both the structure and electrochemical properties of Li[Co_xNi_yMn_1?x?y]O₂ have been investigated by X-ray diffraction and electrochemical tests. The products demonstrated a rather stable cycling behavior, with a reversible capacity of 118 mAh/g for the layered material with Co/Ni/Mn = 1/1/1.     

Highly dispersed Mn2O3 microspheres: Facile solvothermal synthesis and their application as Li-ion battery anodes

Nanostructured transition metal oxides are promising alternative anodes for lithium ion batteries. Li-ion storage performance is expected to improve if high packing density energy particles are available. Herein, Mn₂O₃ microspheres with a ca. 18 μm diameter and a tapped density of 1.33 g/cm³ were synthesized by a facile solvothermal–thermal coversion route. Spherical MnCO₃ precursors were obtained through solvothermal treatment and they decomposed and converted into Mn₂O₃ microspheres at an annealing temperature of 700 °C. The Mn₂O₃ microspheres consisted of Mn₂O₃ nanoparticles with an average 40 nm diameter. These porous Mn₂O₃ microspheres allow good electrolyte penetration and provide an ion buffer reservoir to ensure a constant electrolyte supply. The Mn₂O₃ microspheres have reversible capacities of 590 and 320 mAh/g at 50 and 400 mA/g, respectively. We thus report an efficient route for the fabrication of energy particles for advanced energy storage.     

Mesoporous composite of LiFePO4 and carbon microspheres as positive-electrode materials for lithium-ion batteries

Mesoporous LiFePO₄/C microspheres consisting of LiFePO₄ nanoparticles are successfully fabricated by an eco-friendly hydrothermal approach combined with high-temperature calcinations using cost-effective LiOH and Fe³⁺ salts as raw materials. In this strategy, pure mesoporous LiFePO₄ microspheres, which are composed of LiFePO₄ nanoparticles, were uniformly coated with carbon (∼1.5 nm). Benefiting from this unique architecture, these mesoporous LiFePO₄/C microspheres can be closely packed, having high tap density. The initial discharge capacity of LiFePO₄/C microspheres as positive-electrode materials for lithium-ion batteries could reach 165.3 mAh/g at 0.1 C rate, which is notably close to the theoretical capacity of LiFePO₄ due to the large BET surface area, which provides for a large electrochemically available surface for the active material and electrolyte. The material also exhibits high rate capability (∼100 mAh/g at 8 C) and good cycling stability (capacity retention of 92.2% after 400 cycles at 8 C rate).     

Solid-state synthesis of Li[Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08)]O_2 cathode materials for lithium-ion batteries

Layered Li|Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08]O_2 cathode materials were synthesized via a solid-state reaction for Liion batteries,in which lithium hydroxide monohydrate,manganese dioxide,nickel monoxide,and cobalt monoxide were employed as metal precursors.To uncover the relationship between the structure and electrochemical properties of the materials,synthesis conditions such as calcination temperature and time as well as quenching methods were investigated.For the synthesized Li[Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08)]O_2materials,the metal components were found to be in the form of Mn~(4+),Ni~(2+),and Co~(3+),and their molar ratio was in good agreement with stoichiometric ratio of 0.56:0.16:0.08.Among them,the one synthesized at 800 C for 12 h and subsequently quenched in air showed the best electrochemical performances,which had an initial discharge specific capacity and coulombic efficiency of 265.6 mAh/g and 84.0%,respectively,and when cycled at 0.5,1,and 2C,the corresponding discharge specific capacities were 237.3,212.6.and 178.6 mAh/g,respectively.After recovered to 0.1 C rate,the discharge specific capacity became259.5 mAh/g and the capacity loss was only 2.3% of the initial value at 0.1 C.This work suggests that the solid-state synthesis route is easy for preparing high performance Li[Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08)]O_2 cathode materials for Li-ion batteries.     

Preparation of FeCo-, FeNi- and NiCo-alloy coated cenosphere composites by heterogeneous precipitation

Precursors of binary alloy (Fe_1/2Co_1/2, Fe_1/2Ni_1/2, Ni_1/2Co_1/2, hereinafter referred to as FeCo, FeNi, NiCo) coated cenospheres were prepared by heterogeneous precipitation under optimized conditions. Magnetic binary alloy coated cenosphere composites with core–shell structure were subsequently obtained by thermal reduction of the as-prepared precursors at 700 °C for 2 h under H₂/N₂ atmosphere. The results showed that the alloy coatings were uniform and the binary alloy coated cenosphere composites basically retained the spherical morphology, suggesting that the thickness of the alloy coating could be adjusted to fabricate core–shell composites with multilayer structures. The composites exhibited higher coercivity than the pure alloy powders, and could therefore be used for high-performance functional materials and devices.     

Preparation and electrochemical performance of carbon-coated LiFePO4/LiMnPO4-positive material for a Li-ion battery

Lithium iron phosphate (LiFePO₄)/lithium manganese phosphate (LiMnPO₄)-positive material was successfully prepared through ball milling and high-temperature sintering using manganese acetate, lithium hydroxide, ammonium dihydrogen phosphate, and ferrous oxalate as raw materials. The as-prepared samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, a constant current charge–discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The effects of lithium iron phosphate coating were also discussed. Because of its special core–shell structure, the as-prepared LiMn_0.7Fe_0.3PO₄–LiFePO₄–C exhibits excellent electrochemical performance. The discharge capacity reached 136.6 mAh/g and the specific discharge energy reached 506.9 Wh/kg at a rate of 0.1 C.     

Preparation and Li+ storage properties of hierarchical hollow porous carbon spheres

Hollow ordered porous carbon spheres (HOPCS) with a hierarchical structure were prepared by templating with hollow ordered mesoporous silica spheres (HOMSS). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that HOPCS exhibited a spherical hollow morphology. High-resolution TEM, small angle X-ray diffraction (SAXRD) and N₂ sorption measurements confirmed that HOPCS inversely replicated the unconnected hexagonal-stacked pore structure of HOMSS, and possessed ordered porosity. HOPCS exhibited a higher storage capacity for Li⁺ ion battery (LIB) of 527.6 mA h/g, and good cycling performance. A large capacity loss during the first discharge–charge cycle was found attributed to the high content of micropores. The cycling performance was derived from the hierarchical structure.     

Influences of ions and temperature on performance of carbon nano-particulates in supercapacitors with neutral aqueous electrolytes

A commercial product of carbon nano-particles, Cabot MONACH 1300 pigment black (CMPB), was studied for basic structural information and electrochemical performance in neutral aqueous electrolytes, aiming at applications in supercapacitors. As confirmed by SEM and HRTEM, the CMPB had a hierarchical structure, containing basic 10 nm nano-spheres which combined into ca. 50 nm agglomerates which further aggregated into larger particles of micrometres. The capacitance of this commercial material was found to increase with decreasing the size of hydrous cation (Li⁺ → Na⁺ → K⁺), instead of the cation crystal radius (K⁺ → Na⁺ → Li⁺) when coupled with the same anion (Cl⁻). In electrolytes with the same cation concentration (K⁺), changing the anion from the larger dianion (SO₄²⁻) to the smaller monoanion (Cl⁻) also increased the capacitance at high potential scan rates (>50 mV/s). Increasing electrolyte concentration produced expected effect, including raising the electrode capacitance, but lowering the equivalent series resistance (ESR), charge transfer resistance (CTR), and the diffusion resistance. At higher temperatures, the CMPB exhibited slightly higher capacitance, which does not agree with the Gouy–Chapman theory on electric double layer (EDL). A hypothesis is proposed to account for the capacitance increase with temperature as a result of the CMPB opening up some micro-pores for more ions to access in response to the temperature increase.     

Emission of organic carbon,elemental carbon and water-soluble ions from crop straw burning under flaming and smoldering conditions

Emissions from major agricultural residues were measured using a self-designed combustion system. Emission factors (EFs) of organic carbon (OC), elemental carbon (EC), and water-soluble ions (WSIs) (K⁺, NH₄⁺, Na⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₃⁻, SO₄^2–) in smoke from wheat and rice straw were measured under flaming and smoldering conditions. The OC₁/TC (total carbon) was highest (45.8% flaming, 57.7% smoldering) among carbon fractions. The mean EFs for OC (EF_OC) and EC (EF_EC) were 9.2 ± 3.9 and 2.2 ± 0.7 g/kg for wheat straw and 6.4 ± 1.9 and 1.1 ± 0.3 g/kg for rice straw under flaming conditions, while they were 40.8 ± 5.6 and 5.8 ± 1.0 g/kg and 37.6 ± 6.3 and 5.0 ± 1.4 g/kg under smoldering conditions, respectively. Higher EC ratios were observed in particulate matter (PM) mass under flaming conditions. The OC and EC for the two combustion patterns were significantly correlated (p < 0.01, R = 0.95 for wheat straw; p < 0.01, R = 0.97 for rice straw), and a higher positive correlation between OC₃ and EC was observed under both combustion conditions. WSIs emitted from flaming smoke were dominated by Cl⁻ and K⁺, which contributed 3.4% and 2.4% of the PM mass for rice straw and 2.2% and 1.0% for wheat straw, respectively. The EFs of Cl⁻ and K⁺ were 0.73 ± 0.16 and 0.51 ± 0.14 g/kg for wheat straw and 0.25 ± 0.15 and 0.12 ± 0.05 g/kg for rice straw under flaming conditions, while they were 0.42 ± 0.28 and 0.12 ± 0.06 g/kg and 0.30 ± 0.27 and 0.05 ± 0.03 g/kg under smoldering conditions, respectively. Na⁺, Mg²⁺, and NH₄⁺ were vital components in PM, comprising from 0.8% (smoldering) to 3.1% (flaming) of the mass. Strong correlations of Cl⁻ with K⁺, NH₄⁺, and Na⁺ ions were observed in rice straw and the calculated diagnostic ratios of OC/EC, K⁺/Na⁺ and Cl⁻/Na⁺ could be useful to distinguishing crop straw burning from other sources of atmospheric pollution.     

Effects of multi-dopants (Zn and Ho) in stabilizing spinel structure for cathode materials in lithium rechargeable batteries—Novel chelated sol–gel synthesis

Multi-doped spinels, namely LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ (x = 0.10–0.18; y = 0.02–0.10), for use as cathode materials for lithium-ion rechargeable batteries were synthesized via sol–gel method, using lauric acid as the chelating agent, to obtain micron-sized particles. The physical properties of the synthesized samples were investigated using differential thermal analysis, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, energy-dispersive X-ray analysis, and electrochemical methods. XRD showed that LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ have high degrees of crystallinity and good phase purities. The SEM images of LiMn₂O₄ showed an ice-cube morphology with particles of size 1 μm. Charge–discharge studies showed that undoped LiMn₂O₄ delivered the discharge capacity of 124 mA h/g with coulombic efficiency of 95% during the first cycle, whereas doped spinels delivered discharge capacities of 125, 120, and 127 mA h/g in the first cycle with coulombic efficiencies of 96%, 91%, and 91%, respectively.     

Effects of cerium incorporation on the catalytic oxidation of benzene over flame-made perovskite La1−xCexMnO3 catalysts

Perovskite-type La_1−xCe_xMnO₃ (x = 0–10%) catalysts were prepared by flame spray pyrolysis and their activities during the catalytic oxidation of benzene were examined over the temperature range of 100–450 °C. The structural properties and reducibility of these materials were also characterized by X-ray diffraction (XRD), N₂ adsorption/desorption, H₂ temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). The incorporation of Ce was found to improve the benzene oxidation activity, and the perovskite in which x was 0.1 exhibited the highest activity. Phase composition and surface elemental analyses indicated that non-stoichiometric compounds were present. The incorporation of Ce had a negligible effect on the specific surface area of the perovskites and hence this factor has little impact on the catalytic activity. Introduction of Ce⁴⁺ resulted in modification of the chemical states of both B-site ions and oxygen species and facilitated the reducibility of the perovskite. The surface Mn⁴⁺/Mn³⁺ ratio was increased as a result of Ce⁴⁺ substitution, while a decrease in the surface-adsorbed O/lattice O (O_ads/O_latt) ratio was observed. The relationship between the surface elemental ratios and catalytic activity was established to allow a better understanding of the process by which benzene is oxidized over perovskites.     

Surface responses induced by point load or uniform traction moving steadily on an anisotropic half-plane

Surface responses induced by point load or uniform traction moving steadily with subsonic speed on an anisotropic half-plane boundary are investigated. It is found that the effects of the material constant on surface displacements are through matrices L^?1(v) and S(v)L^?1(v), while those on surface stress components are through matrices Ω(v) and Γ(v). Explicit expressions for the elements of these four matrices are expressed in terms of elastic stiffness for general anisotropic materials. The special cases of monoclinic materials with symmetry plane at x₁ = 0, x₂ = 0 and x₃ = 0, and the case for orthotropic materials are all deduced. Results for isotropic material may be recovered from present results. For monoclinic materials with a plane of symmetry at x₃ = 0, two of the elements of matrix Ω(v) are found to be independent of subsonic speed.     

Magnetic and electrochemical behavior of rhombohedral α-Fe2O3 nanoparticles with (1 0 4) dominant facets

Uniform rhombohedral α-Fe₂O₃ nanoparticles, ～60 nm in size, were synthesized via a triphenylphosphine-assisted hydrothermal method. Scanning electron micrograph (SEM) and transmission electron micrograph (TEM) analyses showed that the as-synthesized rhombohedral nanoparticles were enclosed by six (1 0 4) planes. The concentration of triphenylphosphine played an important role in morphological evolution of the α-Fe₂O₃ nanoparticles. The as-prepared rhombohedral nanoparticles possessed remanent magnetization M_r of 2.6 × 10^?3 emu/g and coercivity H_C of 2.05 Oe, both lower than those of other α-Fe₂O₃ particles with similar size, indicating their potential applications as superparamagnetic precursor materials. Furthermore, these rhombohedral α-Fe₂O₃ nanoparticles exhibited good sensor capability toward H₂O₂ with a linear response in the concentration range of 2–20 mM.     

Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries

We synthesized LiMnPO₄/C with an ordered olivine structure by using a microwave-assisted polyol process in 2:15 (v/v) water–diethylene glycol mixed solvents at 130 °C for 30 min. We also studied how three surfactants—hexadecyltrimethylammonium bromide, polyvinylpyrrolidone k30 (PVPk30), and polyvinylpyrrolidone k90 (PVPk90)—affected the structure, morphology, and performance of the prepared samples, characterizing them by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, charge/discharge tests, and electrochemical impedance spectroscopy. All the samples prepared with or without surfactant had orthorhombic structures with the Pnmb space group. Surfactant molecules may have acted as crystal-face inhibitors to adjust the oriented growth, morphology, and particle size of LiMnPO₄. The microwave effects could accelerate the reaction and nucleation rates of LiMnPO₄ at a lower reaction temperature. The LiMnPO₄/C sample prepared with PVPk30 exhibited a flaky structure coated with a carbon layer (∼2 nm thick), and it delivered a discharge capacity of 126 mAh/g with a capacity retention ratio of ∼99.9% after 50 cycles at 1C. Even at 5C, this sample still had a high discharge capacity of 110 mAh/g, demonstrating good rate performance and cycle performance. The improved performance of LiMnPO₄ likely came from its nanoflake structure and the thin carbon layer coating its LiMnPO₄ particles. Compared with the conventional polyol method, the microwave-assisted polyol method had a much lower reaction time.     

Microwave-hydrothermal preparation of a graphene/hierarchy structure MnO2 composite for a supercapacitor

Graphene/hierarchy structure manganese dioxide (GN/MnO₂) composites were synthesized using a simple microwave-hydrothermal method. The properties of the prepared composites were analyzed using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) measurements. The electrochemical performances of the composites were analyzed using cyclic voltammetry, electrochemical impedance spectrometry (EIS), and chronopotentiometry. The results showed that GN/MnO₂ (10 wt% graphene) displayed a specific capacitance of 244 F/g at a current density of 100 mA/g. An excellent cyclic stability was obtained with a capacity retention of approximately 94.3% after 500 cycles in a 1 mol/L Li₂SO₄ solution. The improved electrochemical performance is attributed to the hierarchy structure of the manganese dioxide, which can enlarge the interface between the active materials and the electrolyte. The preparation route provides a new approach for hierarchy structure graphene composites; this work could be readily extended to the preparation of other graphene-based composites with different structures for use in energy storage devices.     

Observation and analysis of near-surface atmospheric aerosol optical properties in urban Beijing

Year-round measurements of the mass concentration and optical properties of fine aerosols (PM_2.5) from June 2009 to May 2010 at an urban site in Beijing were analyzed. The annual mean values of the PM_2.5 mass concentration, absorption coefficient (Ab), scattering coefficient (Sc) and single scattering albedo (SSA) at 525 nm were 67 ± 66 μg/m³, 64 ± 62 Mm⁻¹, 360 ± 405 Mm⁻¹ and 0.82 ± 0.09, respectively. The bulk mass absorption efficiency and scattering efficiency of the PM_2.5 at 525 nm were 0.78 m²/g and 5.55 m²/g, respectively. The Ab and Sc showed a similar diurnal variation with a maximum at night and a minimum in the afternoon, whereas SSA displayed an opposite diurnal pattern. Significant increases in the Ab and Sc were observed in pollution episodes caused by the accumulation of pollutants from both local and regional sources under unfavorable weather conditions. Aerosol loadings in dust events increased by several times in the spring, which had limited effects on the Ab and Sc due to the low absorption and scattering efficiency of dust particles. The frequency of haze days was the highest in autumn because of the high aerosol absorption and scattering under unfavorable weather conditions. The daily PM_2.5 concentration should be controlled to a level lower than 64 μg/m³ to prevent the occurrence of haze days according to its exponentially decreased relationship with visibility.     

Chemical characteristics of PM2.5 during haze episodes in the urban of Fuzhou,China

Atmospheric fine particles (PM_2.5) were collected in this study with middle volume samplers in Fuzhou, China, during both normal days and haze days in summer (September 2007) and winter (January 2008). The concentrations, distributions, and sources of polycyclic aromatic hydrocarbons (PAHs), organic carbon (OC), elemental carbon (EC), and water soluble inorganic ions (WSIIs) were determinated. The results showed that the concentrations of PM_2.5, PAHs, OC, EC, and WSIIs were in the orders of haze > normal and winter > summer. The dominant PAHs of PM_2.5 in Fuzhou were Fluo, Pyr, Chr, BbF, BkF, BaP, BghiP, and IcdP, which represented about 80.0% of the total PAHs during different sampling periods. The BaPeq concentrations of ∑PAHs were 0.78, 0.99, 1.22, and 2.43 ng/m³ in summer normal, summer haze, winter normal, and winter haze, respectively. Secondary pollutants (SO₄^2?, NO₃^?, NH₄⁺, and OC) were the major chemical compositions of PM_2.5, accounting for 69.0%, 55.1%, 63.4%, and 64.9% of PM_2.5 mass in summer normal, summer haze, winter normal, and winter haze, respectively. Correspondingly, secondary organic carbon (SOC) in Fuzhou accounted for 20.1%, 48.6%, 24.5%, and 50.5% of OC. The average values of nitrogen oxidation ratio (NOR) and sulfur oxidation ratio (SOR) were higher in haze days (0.08 and 0.27) than in normal days (0.05 and 0.22). Higher OC/EC ratios were also found in haze days (5.0) than in normal days (3.3). Correlation analysis demonstrated that visibility had positive correlations with wind speed, and negative correlations with relative humidity and major air pollutants. Overall, the enrichments of PM_2.5, OC, EC, SO₄^2?, and NO₃^? promoted haze formation. Furthermore, the diagnostic ratios of IcdP/(IcdP + BghiP), IcdP/BghiP, OC/EC, and NO₃^?/SO₄^2? indicated that vehicle exhaust and coal consumption were the main sources of pollutants in Fuzhou.     

Real-time measurements of PM2.5, PM10–2.5, and BC in an urban street canyon

A continuous dichotomous beta gauge monitor was used to characterize the hourly content of PM_2.5, PM_10–2.5, and Black Carbon (BC) over a 12-month period in an urban street canyon of Hong Kong. Hourly vehicle counts for nine vehicle classes and meteorological data were also recorded. The average weekly cycles of PM_2.5, PM_10–2.5, and BC suggested that all species are related to traffic, with high concentrations on workdays and low concentrations over the weekends. PM_2.5 exhibited two comparable concentrations at 10:00–11:00 (63.4 μg/m³) and 17:00–18:00 (65.0 μg/m³) local time (LT) during workdays, corresponding to the hours when the numbers of diesel-fueled and gasoline-fueled vehicles were at their maximum levels: 3179 and 2907 h⁻¹, respectively. BC is emitted mainly by diesel-fueled vehicles and this showed the highest concentration (31.2 μg/m³) during the midday period (10:00–11:00 LT) on workdays. A poor correlation was found between PM_2.5 concentration and wind speed (R = 0.51, P-value > 0.001). In contrast, the concentration of PM_10–2.5 was found to depend upon wind speed and it increased with obvious statistical significance as wind speed increased (R = 0.98, P-value < 0.0001).     

Chemical characteristics of PM2.5 during dust storms and air pollution events in Chengdu,China

Daily fine particulate (PM_2.5) samples were collected in Chengdu from April 2009 to February 2010 to investigate their chemical profiles during dust storms (DSs) and several types of pollution events, including haze (HDs), biomass burning (BBs), and fireworks displays (FDs). The highest PM_2.5 mass concentrations were found during DSs (283.3 μg/m³), followed by FDs (212.7 μg/m³), HDs (187.3 μg/m³), and BBs (130.1 μg/m³). The concentrations of most elements were elevated during DSs and pollution events, except for BBs. Secondary inorganic ions (NO₃^?, SO₄^2?, and NH₄⁺) were enriched during HDs, while PM_2.5 from BBs showed high K⁺ but low SO₄^2?. FDs caused increases in K⁺ and enrichment in SO₄^2?. Ca²⁺ was abundant in DS samples. Ion-balance calculations indicated that PM_2.5 from HDs and FDs was more acidic than on normal days, but DS and BB particles were alkaline. The highest organic carbon (OC) concentration was 26.1 μg/m³ during FDs, followed by BBs (23.6 μg/m³), HDs (19.6 μg/m³), and DSs (18.8 μg/m³). In contrast, elemental carbon (EC) concentration was more abundant during HDs (10.6 μg/m³) and FDs (9.5 μg/m³) than during BBs (6.2 μg/m³) and DSs (6.0 μg/m³). The highest OC/EC ratios were obtained during BBs, with the lowest during HDs. SO₄^2?/K⁺ and TCA/SO₄^2? ratios proved to be effective indicators for differentiating pollution events. Mass balance showed that organic matter, SO₄^2?, and NO₃^? were the dominant chemical components during pollution events, while soil dust was dominant during DSs.