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.     

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.     

Open-pore LiFePO4/C microspheres with high volumetric energy density for lithium ion batteries

LiFePO₄/C microspheres with different surface morphologies and porosities were prepared from different carbon sources. The effects of the surface morphology and pore structure of the microspheres on their electrochemical properties and electrode density were investigated. The electrochemical performance and electrode density depended on the morphology and pore structure of the LiFePO₄/C microspheres. Open-pore LiFePO₄/C microspheres with rough surfaces exhibited good adhesion with current collectors and a high electrode density (2.6 g/cm³). They also exhibited high performance in a half cell and full battery with a high volumetric energy density.     

Solid-state synthesis of Li[Li0.2Mn0.56Ni0.16Co0.08]O2 cathode materials for lithium-ion batteries

Layered Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials were synthesized via a solid-state reaction for Li-ion 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_0.2Mn_0.56Ni_0.16Co_0.08]O₂ materials, the metal components were found to be in the form of Mn⁴⁺, Ni²⁺, and Co³⁺, 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 2 C, 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 became 259.5 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_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials for Li-ion batteries.     

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（1.5nm）.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）.     

Fabrication of magnetic nanosized γ-FeNi-coated ceramic core–shell microspheres by heterogeneous precipitation and thermal reduction

Precursors with NiCO₃·2Ni(OH)₂·2H₂O- and Fe₂O₃·nH₂O-coated alumina, graphite and cenosphere were synthesized by precipitation using ferrous sulfate, nickel sulfate, ammonium bicarbonate, alumina, graphite and cenosphere as the main starting materials. Magnetic γ-FeNi-coated alumina, graphite and cenosphere core–shell structural microspheres were subsequently prepared by thermal reduction of the as-prepared precursors at 600 °C for 2 h. Precipitation parameters, e.g. concentration of ceramic micropowders (10 g/L), sulfate solution (0.2 mol/L), rate of adding reactants (3 mL/min) and pH value were optimized by a trial-and-error method. Powders of the precursors and the resulting coating of γ-FeNi with grain size below 40 nm on alumina, graphite and cenosphere microspheres were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The magnetic properties of the nanosize γ-FeNi-coated alumina, graphite and cenosphere microspheres were measured by vibrating sample magnetometer (VSM). The results show that the core–shell structural γ-FeNi-coated ceramic microspheres exhibited higher coercivity than pure γ-FeNi powders, indicating that these materials can be used for high-performance functional materials and devices.     

Electrochemical performance of polygonized carbon nanofibers as anode materials for lithium-ion batteries

Carbon nanofibers with a polygonal cross section (P-CNFs) synthesized using a catalytic chemical vapor deposition (CCVD) technology have been investigated for potential applications in lithium batteries as anode materials. P-CNFs exhibit excellent high-rate capabilities. At a current density as high as 3.7 and 7.4 A/g, P-CNFs can still deliver a reversible capacity of 198.4 and 158.2 mAh/g, respectively. To improve their first coulombic efficiency, carbon-coated P-CNFs were prepared through thermal vapor deposition (TVD) of benzene at 900 °C. The electrochemical results demonstrate that appropriate amount of carbon coating can improve the first coulombic efficiency, the cycling stability and the rate performance of P-CNFs. After carbon coating, P-CNFs gain a weight increase approximately by 103 wt%, with its first coulombic efficiency increasing from 63.1 to 78.4%, and deliver a reversible capacity of 197.4 mAh/g at a current density of 3.7 A/g. After dozens of cycles, there is no significant capacity degradation at both low and high current densities.     

Large-scale synthesis of hierarchical MnO2 for benzene catalytic oxidation

Hierarchical sea-urchin-shaped manganese oxide microspheres were synthesized via a facile method based on the reaction between KMnO₄ and MnSO₄ in HNO₃ solution at 50 °C. The average diameter of the microspheres is ∼850 nm. The microspheres consist of a core of diameter of ∼800 nm and nanorods of width ∼50 nm. The nanorods exist at the edge of the core. The Brunauer–Emmett–Teller surface area of the sea-urchin-shaped microspheres is 259.4 m²/g. A possible formation mechanism of the hierarchical sea-urchin-shaped microspheres is proposed. The temperature for 90% conversion of benzene (T_90%) on the hierarchical urchin-shaped MnO₂ microspheres is about 218 °C.     

Synthesis of mesoporous γ-AlOOH@Fe3O4 magnetic nanomicrospheres

Mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres were synthesized using superparamagnetic Fe₃O₄ nanoparticles as the core and aluminum isopropoxide (AIP) as the aluminum source. The obtained magnetic nanomicrospheres were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N₂ adsorption–desorption and vibrating sample magnetometry (VSM). The effects of preparation parameters such as hydrolysis time of AIP, concentration of AIP and coating layer number on microspheres were investigated. The results indicated that the mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres consisted of a mesoporous γ-AlOOH shell and a Fe₃O₄ magnetic core. The diameter of γ-AlOOH@Fe₃O₄ nanomicrospheres was about 200 nm, the thickness of mesoporous γ-AlOOH shell was about 5 nm and the average pore size was 3.8 nm. The thickness of the mesoporous γ-AlOOH shell could be controlled via layer-by-layer coating times. The formation mechanism of the mesoporous γ-AlOOH shell involved a “chemisorption–hydrolysis” process.     

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.     

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.     

Capture of phosphates in surface water by TiO2 nanoparticles under UV irradiation

The capture of orthophosphates and total phosphorus from the Pudong Canal river in the Pudong District of Shanghai by TiO₂ nanoparticles is studied using a rotating photoreactor and the nano-TiO₂ photocatalyst Degussa P25. The effects of UV irradiation intensity in a range of 20–74 mW/cm², the loading of the TiO₂ nanoparticles in a range of 0.05–0.1 g/L, irradiation time up to 4 h, and pH values in a range of 2–10.5 on the capture efficiency are investigated. The results show that the capture of orthophosphates and total P are significantly enhanced by UV irradiation; at a loading of 0.1 g/L and an irradiation intensity above 36 mW/cm², orthophosphates and total phosphorus are rapidly captured by TiO₂ nanoparticles, causing an observed reduction from 0.4 mg/L down to 0.02 mg/L. pH values in a range of 2–10.5 have little effect on the capture efficiency of orthophosphates and total phosphorus.     

Composition and morphology of the thermal decomposition products of 3Mg(OH)2·MgCl2·8H2O nanowires

The thermal decomposition of 3Mg(OH)₂·MgCl₂·8H₂O (318MHCH) nanowires synthesized from agglomerated Mg(OH)₂ microspheres was investigated. The influence of heating rate and temperature on the composition and morphology of the products was investigated. Thermogravimetric-differential scanning calorimetry, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray diffraction showed that increasing the heating rate from 1 to 20 °C/min promoted the escape of crystalline water from the 318MHCH nanowires. 318MHCH nanowires were dehydrated stepwise to 310MHCH porous nanowires from room temperature to 320 °C, and then to MgO cubic nanoparticles from 420 to 700 °C. The nanowires retained their one-dimensional morphology, until the phase changed to MgO. The immediate collapse of the one-dimensional structure was attributed to the presence of Mg–O/Cl chains.     

Chemically modified magnetic chitosan microspheres for Cr(VI) removal from acidic aqueous solution

A bioadsorbent composed of magnetic silica nanoparticles encapsulated by chitosan microspheres was prepared by the emulsion cross-linking method, and it was then modified with quaternary ammonium groups by reaction with ethylenediamine and glycidyl trimethylammonium chloride. Characterization of the bioadsorbent indicated that it was highly acid resistant and magnetically responsive. The bioadsorbent was then used to remove Cr(VI) from acidic aqueous solution. The results of batch experiments indicated that the optimal pH value was 2.5, and the adsorbent exhibited low pH dependence. The maximum adsorption capacity was 233.1 mg/g at pH 2.5 and 25 °C, and the equilibrium time was determined to be 40–120 min depending on the initial Cr(VI) concentration. The adsorbent could be effectively regenerated using a mixture of 0.3 mol/L NaOH and 0.3 mol/L NaCl with a desorption efficiency of 95.6%, indicating high reusability. In conclusion, the bioadsorbent shows potential for Cr(VI) removal from acidic wastewater.     

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.     

Effect of calcining temperature and time on the characteristics of Sb-doped SnO2 nanoparticles synthesized by the sol–gel method

Spherical Sb-doped SnO₂ (ATO) nanoparticles were synthesized by the sol–gel route, employing SnCl₄·5H₂O and SbCl₃ as precursors in an ethanol solution. The influences of the calcining temperature and calcining time on the crystallite size, crystallinity, lattice parameters, lattice distortion ratio and the resistivity of the ATO nanoparticles were synthetically investigated. The results suggested that the ATO nanoparticles were crystallized in a tetragonal cassiterite structure of SnO₂ with a highly (1 1 0)-plane-preferred orientation. The calcining temperature had a dominating effect on the crystallite size, crystallinity, lattice distortion ratios and resistivity of the ATO. As the calcining temperature increased, the average crystallite size increased, the crystallinity was promoted accompanied by a decrease in the lattice distortion ratio and a corresponding decrease in the resistivity of the ATO. X-ray diffraction (XRD) and Fourier transform infrared spectrophotometer (FTIR) analysis revealed that Sb ions could not entirely supplant the Sn ions in the SnO₂ lattice for a calcining time of less than 0.5 h, even at a calcining temperature of 1000 °C. The ATO nanoparticles calcined at 1000 °C for 3.0 h possessed the lowest resistivity of 10.18 Ω cm.     

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.     

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.