LiFePO4 batteries with enhanced lithium-ion-diffusion ability due to graphene addition

In this study, graphene was added to LiFePO₄ via a hydrothermal method to improve the lithium-ion-diffusion ability of LiFePO₄. The influence of graphene addition on LiFePO₄ was studied by X-ray diffraction (XRD), field emission scanning electron microscopy, transmission electron microscopy, cyclic voltammetry, cycling test, and AC impedance analysis. The addition of graphene to LiFePO₄ resulted in the formation of a LiFePO₄–graphene composite; XRD observations revealed the composite to have a single phase with an olivine-type structure. Furthermore, LiFePO₄ particles in the composite were stacked on the graphene sheet surface, thereby enabling the composite to form an effective conducting network and facilitate the penetration of the surface of active materials by an electrolyte. The lithium-ion-diffusion ability of the LiFePO₄–graphene composite was greater than that of pure LiFePO₄. Of a number of materials studied [namely, pure LiFePO₄, LiFePO₄–graphene (1 %), LiFePO₄–graphene (5 %), and LiFePO₄–graphene (8 %)], LiFePO₄–graphene (5 %) delivered the best electrochemical performance with a lithium-ion-diffusion coefficient of 8.18 × 10^?12 cm² s^?1 and the highest specific discharge capacity of 149 mAh g^?1 at 0.17 C; in contrast, the corresponding values for pure LiFePO₄ were 3.01 × 10^?12 cm² s^?1 and 109 mAh g^?1, respectively. Further, LiFePO₄–graphene (5 %) showed a very high specific discharge capacity of 170 mAh g^?1 at 0.1 C, which is equal to the theoretical capacity of LiFePO₄.     

Porous ZnO@C core–shell nanocomposites as high performance electrode materials for rechargeable lithium-ion batteries

A novel porous spherical ZnO@carbon (C) nanocomposite based on zeolitic imidazolate frameworks (ZIFs-8)-directed method was prepared for lithium-ion batteries (LIBs). In this strategy, spherical ZnO nanoparticles were firstly prepared, then 2-methylimidazolate and Zn²⁺ were added alternately under ultrasound to fabricate ZnO@ZIF-8. Finally, the novel porous spherical ZnO@C nanocomposites were obtained via pyrolyzing the corresponding ZnO@ZIF-8. The novel porous spherical ZnO@C nanocomposites were characterized with different analysis techniques such as scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction. The resulted spherical ZnO@C nanocomposites exhibited a high reversible capacity of 932 mA h g^?1 at 0.1 A g^?1 after 100 cycles, which is much higher than that of the pure ZnO nanoparticles. The porous structure, high specific surface area and good electrical conductivity eventually contribute to the good performance of the resulted ZnO@C nanocomposites for LIBs should be ascribed to the proous structure and high BET surface area derived from ZIFs, as well as the good electrical conductivity of the amourphous carbon derived from ZIFs.     

Adsorption of Cu(II) from Aqueous Solution by Porous Mn3[Co(CN)6]2 · nH2O Nanospheres

Prussian blue analogue of porous Mn₃[Co(CN)₆]₂ · nH₂O nanospheres with a large surface area were prepared by simple mixing K₃[Co(CN)₆]₂ and manganous nitrate solution at room temperature. The morphology and structure of the prepared products were characterized by XRD, FE-SEM, TEM, and BET. The results indicated that the product was composed of nanospheres with the diameter of ～250 nm, which was of porous structure with the pore diameter in the 2.5–4 nm range. The adsorption behavior of Cu(II) ions from aqueous solution onto porous nanospheres was investigated as a function of parameters, such as the equilibrium time, the pH, the initial concentration, and the temperature. A maximum adsorption capacity of 140.85 mg g^?1 of Cu(II) was achieved. Due to the simple synthetic method and its high adsorption capacity, the porous nanospheres had the potential to be utilized as an effective adsorbent for Cu(II) removal.     

A novel dendritic crystal Co3O4 as high-performance anode materials for lithium-ion batteries

The spinel-type Co₃O₄ with a dendritic nanostructure is prepared via homogeneous co-precipitation method in the presence of oxalic as complex agent. The special structure was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis, which show that the precursor can be transformed into dendritic crystal Co₃O₄ by calcining at 500 °C for 2 h with a diameter of 20–50 nm. Such a three-dimensional interconnected structure used as an anode material for lithium-ion batteries shows that the discharge specific capacity still remains at 951.7 mA h g^?1 after 100 cycles at a current density of 100 mA g^?1. Furthermore, this material also presents a good rate performance; when the current density increases to 1,000, 4,000, and 8,000 mA g^?1, the reversible capacity can render about 1,126.2, 932.3, and 344.2 mA h g^?1, respectively. The excellent electrochemical performance is mainly attributed to the dendritic nanostructure composed of interconnected Co₃O₄ nanoparticles.     

Application of attapulgite/maltose system on mesoporous carbon material preparation for electrochemical capacitors

Mesoporous carbon materials were prepared through atmospheric pressure impregnation at room temperature using attapulgite as hard template and maltose as carbon source. N₂ absorption–desorption, X-ray diffraction, and transmission electron microscopy were used to determine the construction and morphology of the materials. The results showed that the prepared carbon materials possessed chain-layered structures whose surfaces were filled with ample nanoscale apertures. The materials also exhibited partial fasciculus with specific surface area and total pore volume of 628.6 m² g^?1 and 1.31 cm³ g^?1, respectively. Constant current charge/discharge, cyclic voltammetry, and AC impedance tests were performed to evaluate the electrochemical performance of the materials. The constant current charge/discharge tests showed that the materials have excellent energy storage capacity. When the current density was 600 mA g^?1, the specific capacitance value reached 171 F g^?1. The materials showed quasi-rectangular features of typical cyclic voltammetry curve even at high scan rate (200 mV s^?1), indicating that they possess excellent rate capacity. The AC impedance tests showed that the materials were typical porous electrode materials with combination resistance of 0.82 Ω. The specific capacitance of the materials reached 79 % after 1,000 constant current charge/discharge cycles, indicating that they have superior cyclic stability.     

Synthesis and application of amine functionalized silica mesoporous magnetite nanoparticles for removal of chromium(VI) from aqueous solutions

In this research, novel nanoparticles of Kit-6 mesoporous silica magnetite were synthesized with 9.6 nm pore diameter and 241.68 m² g^?1 surface area. The synthesized mesoporous magnetite nanoparticles (MMNPs) were functionalized with amine groups. Scanning electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption–desorption method confirmed the morphology and structure of the synthesized nanoparticles. The amine functionalized MMNPs were used for sorption of toxic chromate ions from aqueous samples. The effect of various experimental parameters (four factors at three levels) on the sorption efficiency of Cr(VI) was studied and optimized via Taguchi L₉ (3⁴) orthogonal array experimental design. At optimum conditions, the sorption of the Cr(VI) was best described by a pseudo second-order kinetic model with R² = 0.9999 and q_eq = 129.8 mg g^?1, suggesting chemisorption mechanism. Adsorption data were fitted well to the Langmuir isotherm and the synthesized sorbent showed complete ion removal with 185.2 mg g^?1sorption capacity.     

Facile fabrication of hollow polyaniline spheres and its application in supercapacitor

Polyaniline (PANI) is a promising electroactive material for pseudocapacitor due to the existence of the electronic conjugation structure. Here we demonstrate a novel approach to prepare hollow polyaniline nanospheres. In this process, uniform poly (methyl methacrylate- butyl methacrylate - methacrylic acid) (PMMA-PBMA-PMAA) latex microspheres as self-sacrificial templates were rapidly prepared through an emulsion polymerization method. Then the hollow PANI (H-PANI) nanospheres were obtained directly through an in-situ chemical oxidative polymerization of aniline in the presence of PMMA-PBMA-PMAA microspheres, which can be explained by the “dissolution” of templates and phase separation between the constituent polymers. The structure and morphology of the nanophase materials have been characterized by field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectra. The specific capacitance of H-PANI is 485.5 F g^?1 at 1 A g^?1 and there is 69% performance attenuation after 500 cycles, which show a promising electrochemical performance.     

Pore size-controlled synthesis of 3D hierarchical porous carbon materials for lithium-ion batteries

3D hierarchical porous carbons (3DCs) with different pore size distributions are prepared by using Ni(OH)₂ as template. The morphology, crystalline features, pore structure and surface composition of the hierarchical porous carbons are characterized using various analytic techniques including scanning electron microscopy, transmission electron microscopy, N₂ physical adsorption, powder X-ray diffraction and X-ray photoelectron spectroscopy. It is found that the pore size distributions of the 3DCs play an important role in the lithium-storage capacity when they are used as anode materials for rechargeable lithium-ion batteries. The typical sample 3DC-20 has a specific reversible capacity of 630 mAh g^??1 in the first cycle and and 363 mAh g^??1 after 50 cycles. The high capacity of 3DC-20 can be attributed to the existence of the largest amount of micropores with 0.6–0.9 nm pore width, which increase the lithium storage capacity; in addition, the existence of mesoporous and macroporous effectively shortens the distance for charge diffusion, the turbostratic graphite structure low resistance for electron conduction.     

Preparation of porous polyvinyl acetate materials using concentrated emulsion templates

This paper is devoted to the preparation of highly porous polyvinyl acetate (PVAc) materials using concentrated emulsion templates. Stable concentrated emulsions were obtained by introducing colloidal silica to the aqueous phase, which was absorbed at the interface of the emulsion preventing the coalescence of the dispersed phase. The prepared samples were characterized by Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), N₂ adsorption (BET), thermo-gravimetric and differential thermal techniques. SEM measurement revealed that cell diameter of the resulting foams was controlled from 1 to 10 μm by altering the emulsion composition, such as the content of colloidal silica, and the volume fraction of the dispersed phase. FT-IR revealed the presence of SiO₂ and PVAc in the resulting foams. The nitrogen adsorption analysis showed that the samples possessed mesoporous structure with surface areas lager than 62 m² g^?1. Porous PVAc materials, which are biocompatible, will have potential applications in area of life science.     

Effect of particle shape on the electrochemical properties of CaSnO3 as an anode material for lithium-ion batteries

Cubic and star-shaped CaSnO₃ particles with a perovskite structure were synthesized successfully using a simple hydrothermal method at a low temperature of 140 °C. The structure and morphology of the CaSnO₃ powders were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical properties of the CaSnO₃ as anode materials for lithium-ion batteries were tested by constant current discharge/charge and cyclic voltammetry. The large irreversible capacity in the initial cycle was similar to that of tin oxide, due to the decomposition of tin oxide into metallic tin and Li₂O, followed by a reversible Li–Sn formation. The reversible capacity of the cubic CaSnO₃ was 382 mAh g^?1 in the first cycle and was maintained at 365 mAh g^?1 in the following cycles. The cubic CaSnO₃ particles had a higher reversible capacity than the star-shaped CaSnO₃ particles and retained a capacity of about 365 mAh g^?1 after 60 cycles as well as good cycle stability, showing potential as attractive anode materials for lithium-ion batteries. It is found that the particle shape had a marked effect on electrochemical performance.     

Surfactant-free microwave hydrothermal synthesis of SnO2 nanosheets as an anode material for lithium battery applications

SnO₂ nanosheets were synthesized using microwave hydrothermal method without using a surfactant and organic solvents. Formation of pure nanocrystalline rutile phase of SnO₂ sample was confirmed by X-ray diffraction (XRD) results and the average crystallite size of SnO₂ sample calculated using Scherrer's formula and XRD data is found to be 6 nm. HR-TEM, SAED and EDX results showed the formation of agglomerated nanosize sheets like morphology with high porous structured SnO₂ powder. Further, the formation of high porous structured SnO₂ powder was confirmed from BET surface area results (59.28 m² g^?1). The electrochemical performance of the lithium-ion battery made up of SnO₂ nanosheets, as an anode, was tested through the cyclic voltammetry and galvanostatic charge-discharge measurements. The galvanostatic charge-discharge results of the lithium-ion battery showed good discharge capacity of 257.8 mAh g^?1 after 50 cycles at a current density of 100 mA g^?1. The improved electrochemical properties may be due to the formation of a unique nanosize sheets type morphology with high porous structured SnO₂ powder. High porous structured nanosize sheets type morphology of SnO₂ can help to reduce the diffusion length and sustain the volume changes during the charging-discharging process.Hence, high porous structured nanosize sheets morphology of SnO₂ prepared using the microwave hydrothermal method without using a surfactant and organic solvents can be a better anode material for lithium ion battery applications.     

One-pot synthesis of wormhole-like mesostructured silica with a high amine loading for enhanced adsorption of clofibric acid

A series of ordered amine-functionalized hexagonal mesoporous silicas (HMS-NH₂) were synthesized successfully via direct co-condensation using dodecylamine as a structure-directing agent in the presence of 3-aminopropyltrimethoxysilane (APS), [aminoethylamino]propyltrimethoxysilane or [(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEEA) as amine group precursors. Tetrahydrofuran was used as the organic solvent to control the interaction and sol–gel reaction of the silica source and aminosilanes. The effect of the type and concentration of the added aminosilanes on the physicochemical properties of the resulting HMS-NH₂ materials were investigated. Thermogravimetric analysis, Fourier-transform infrared spectroscopy and solid-state ²⁹Si nuclear magnetic resonance spectroscopy confirmed a successful functionalization of the HMS surface with different amine groups. X-ray diffraction and transmission electron microscopy indicated that their wormhole-like mesostructured framework was retained after functionalization at a high APS loading level (15 mol%) or using AEEA as the aminosilane precursor. A high degree (88–98%) of aminosilanes was incorporated into the HMS framework, corresponding to an amine concentration of 0.72–2.16 mmol g^?1. The HMS-NH₂ materials had a high surface area (272–627 m² g^?1), a large total pore volume (0.48–1.92 cm³ g^?1) and exhibited an enhanced adsorption capacity for clofibric acid in aqueous solution.     

Mesoporous TiO<Subscript>2</Subscript> microspheres synthesized via a facile hydrothermal method for dye sensitized solar cell applications

Mesoporous TiO₂ microspheres were successfully synthesized by a facile hydrothermal process and the obtained product was sintered at 450 °C. The sintered TiO₂ powder was characterised by powder X-ray diffraction pattern and the result shows pure anatase phase with good crystalline nature. The morphological image of field emission scanning electron microscopy and high resolution transmission electron microscopy shows spherical shape and size of the particles is around 100 to 300 nm. The Brunauer–Emmett–Teller surface area of synthesized TiO₂ material was 56.32 m² g^?1 and average pore width of synthesized materials was 7.1 and 9.3 nm. Bimodal pore structure of TiO₂ microspheres has been very effective for electrolyte diffusion into photoanode in dye sensitized solar cells. The synthesized anatase TiO₂ microsphere based dye sensitized solar cells have high surface area with light scattering effect to enhance the photocurrent and conversion efficiency than the commercial P25 photoanode material. The power conversion efficiency of synthesized mesoporous TiO₂ microspheres and commercial P25 material is 4.2 and 2.7 % respectively. Therefore bimodal mesoporous anatase TiO₂ microsphere appears to be a promising and potential candidate for dye sensitized solar cells (DSSC) application.     

CO<Subscript>2</Subscript> adsorption at high pressures in MCM-41 and derived alkali-containing samples: the role of the textural properties and chemical affinity

The adsorption properties of N₂ and CO₂ of MCM-41 and derived alkali-containing samples were analyzed over a wide range of pressures (up to ~4500 kPa) and temperatures (between 30 and 300 °C). The high-pressure and high-temperature experiments were carried out on pure MCM-41 and K- and Na-impregnated derived samples. It was analyzed the influence of pressure and temperature on the CO₂ capture capacity on pure and impregnated samples. The adsorption performance was correlated to the structure and textural properties of the materials using X-ray diffraction and N₂ adsorption–desorption measurements. The addition of an alkaline element changes the textural properties of the material increasing the pore size, which positively affected the CO₂ adsorption capacity of these materials at high pressure. In addition, the isosteric heats of adsorption gave information about the chemical affinity between the impregnated materials and CO₂. The CO₂ adsorption at ~ 4500 kPa for the samples with 5 wt% Na at 100 and 200 °C were 77.98 and 9.79 mmol g^?1, respectively, while the pure MCM-41 adsorbs only 8.92 mmol g^?1.     

Synthesis of hollow porous carbon nanospheres from coal tar for adsorption of Direct Black 38 dye

A hollow porous carbon nanospheres (HPCNs) material which suits for adsorption of Direct Black 38 (DB38) was prepared from coal tar using zinc acetate as a template coupled with KOH activation. The synthesized HPCNs features with nanospheres structure and contains both micropores and a lot of mesopores. The HPCN_1?4?2 made with the mass weight ratio of coal tar/zinc acetate/KOH at 1:4:2 shows a large surface area of 1374 m² g^?1 with an average pore size of 7.41 nm. The HPCN_1?4?2 exhibits excellent adsorption capacity for DB38 dye, which has big molecular size at room temperature. This is mainly due to its large surface area and pore volumes contributed by its mesopores. This work suggests an effective way to synthesize a high performance adsorbent for large molecular size dyes from low-cost coal tar.     

Impact of microwave synthesis conditions on the rechargeable capacity of LiCoPO4 for lithium ion batteries

Lithium transition metal phosphates have the capability of improving cathode energy densities up to 800 Wh kg^?1, a 27 % increase over conventional cathode active material energy densities. In this study, the effect of base-to-acid (NH₄OH:H₃PO₄) stoichiometric conditions on the intrinsic reversible capacity of lithium cobalt phosphate (LiCoPO₄) active material are investigated through microwave synthesis and electrochemical testing. Variation in solution pH results in an increase of 69 mAh g^?1 in achievable capacity. X-ray diffraction results show highly crystalline LiCoPO₄, with particle sizes ranging from 200 nm to greater than 1 μm based upon scanning electron microscopy. Electrochemical analysis with 1 M LiPF₆ EC:EMC (1:2 v/v) provides the highest capacity over multiple cycles. A discharge capacity of 128 mAh g^?1 (78 % of theoretical capacity) is achievable for intrinsic LiCoPO₄ without further treatment (e.g., carbon coating) at an effective 0.1 C rate with a proper constant current–constant voltage step. Analysis of reported synthesis techniques shows that microwave synthesis yields the highest capacity for the intrinsic LiCoPO₄ material to date.     

Synthesis and optimization of NASICON-type Li3V2(PO4)3 by adipic acid-mediated solid-state approach

We report the synthesis and optimization of NASICON-type carbon-coated Li₃V₂(PO₄)₃ by solid-state approach. Adipic acid (AA) is used as the source material for the carbon. Initially, the synthesis of monoclinic Li₃V₂(PO₄)₃ is optimized at a precalcination temperature of 300 °C for 4 h and 900 °C for 8 h under Ar flow to yield a single phase. Powder characterizations such as thermogravimetric–differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and particle size distribution are conducted, and the results are presented. The AA concentration is varied according to the total metal ion composition in the compound (0.05, 0.1, and 0.15 M). Electrochemical Li-insertion properties are evaluated in half-cell configurations between 3 and 4.8 V vs. Li at a current density of 0.1 mA cm^?2 at room temperature. Compared with the lower AA concentrations, Li/Li₃V₂(PO₄)₃ (0.15 M AA) cell exhibited discharge capacities of 178 and 147 mAh g^?1 for the 1st and 50th cycles, respectively, and a capacity retention of 83 % after 50 cycles, which is 11 % higher than that of the native compound. Li/Li₃V₂(PO₄)₃ (0.15 M AA) showed better rate performances and delivered discharge capacities of 173, 165, 150, 132, 105, and 76 mAh g^?1 at rates of 0.1, 0.2, 0.5, 1, 5, and 12 C, respectively. Electrochemical impedance spectroscopy reveals the enhancement in electronic conductivity profile after carbon coating.     

Preparation,characterization and application of iron (III)-loaded chitosan hollow fiber membranes as a new bio-based As (V) sorbent

Fe (III)-loaded chitosan (CS) hollow fibers (CS-Fe (III) HF) were successfully prepared according to the dry-wet spinning technique. The CS-Fe (III) HFs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA). Removal of pentavalent arsenic was studied through biosorption on CS-Fe (III) HF adsorptive membranes. The response surface methodology (RSM) was applied to investigate the influence of the main operating parameters such as contact time, pH, initial As (V) concentration and HFs dosage on the adsorption capacity of As (V). From the Pareto analysis, pH, [As (V)]_o, [CS-Fe (III) HF membranes] and squared effect of [As(V)]_o were found to produce the largest effect on biosorption of As (V). Kinetic studies showed that the pseudo-second-order kinetic model provides the best correlation to the experimental results. Equilibrium data fitted well with the Langmuir model with maximum adsorption capacity of 3,703 μg g^?1. A laboratory scale glass membrane module consisting of three CS-Fe(III) HFs has also been prepared and tested for biosorption of As (V) at a real scale. Permeability of As (V) ions through the CS-Fe (III) HF membranes was 0.145 μmol m^?2 h^?1 bar ^?1.     

Nostoc calcicola Immobilized in Silica-coated Calcium Alginate and Silica Gel for Applications in Heavy Metal Biosorption

The present study reports the preparation and characterization of silica-based immobilization matrices for the purpose of metal accumulation using immobilized cyanobacterium Nostoc calcicola. Silica gel was prepared using aqueous sodium silicate and colloidal silica. Calcium alginate (CAG) beads were coated with silica using sodium silicate solutions. Microscopy observations and TTC tests confirmed that the immobilized cells were intact and viable. Ultrastructural studies with electron microscopy revealed a membrane thickness of approximately 10 μm around the CAG and the silica gel to be of mesoporous nature. BET surface area of silica gel-immobilized N. calcicola was 160 m² g^?1. The porous volume and average pore diameter were 0.40 cm³ g^?1 and ca. 100 Å, respectively, as calculated using the BJH model. Studies on silica-coated calcium alginate immobilized cells showed that these were superior to the uncoated CAG beads in terms of mechanical strength and metal accumulation. The silica matrices were found to be stable for repeated cycles of metal removal and with commonly used eluants for desorption processes. These matrices have potential applications in immobilization of industrially important biocatalysts.     

Synthesis and application of nanocomposite Fe3O4@SiO2@CTAB–SiO2 as a novel adsorbent for removal of cyclophosphamide from water samples

ABSTRACT

We present a way of synthesizing nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ by employing simple sol–gel technique with selective etching for extreme selectivity adsorption of cyclophosphamide (CP). The transmission electron microscopy (TEM); scanning electron microscopy (SEM); X-ray diffraction (XRD); Fourier transform infrared (FT-IR); vibrating sample magnetometer (VSM); pH_PZC; and Brunauer, Emmett and Teller (BET) techniques were used for nanocomposite characterization. These nanoparticles have an S_BET of 157.8 m² g^?1 and a high saturation magnetization of 67.5 emu g^?1. First, the adsorption system was examined as a function of contact time under various initial CP contents, ionic strength, initial solution pH, adsorbent dose and temperature in batch test. The optimum dose, pH and contact time were obtained to be 0.01 g, 7.0 and 30 min, respectively. Ultimately, experimental isotherm and kinetics data of adsorption of CP onto nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ were fitted to classical models. Additionally, it was found that the maximum adsorption process capacity of CP on adsorbent was 342.8 mg g^?1.