Ultrasonic spray pyrolysis of nano crystalline spinel LiMn2O4 showing good cycling performance in the 3 V range

Spherical lithium manganese oxide spinel was synthesized by an ultrasonic spray pyrolysis method, and has been characterized using X-ray diffraction, scanning electron microscopy, transimission electron microscopy and electrochemical cycling at 3 V regions. The LiMn₂O₄ powders were composed of about 10 nm-sized primary particles. The delivered discharge capacity of the synthesized nano-material was 125 mAh g⁻¹ between 2.4 and 3.5 V and its retention was about 96% upon 50 cycling. From the high resolution transmission electron microscopic study, it was found that structural transition of the parent material did not occur even after the 50th electrochemical cycling on the 3 V region. It seems that the reversible structural change is possible for nanocrystalline LiMn₂O₄ as observed by the X-ray diffraction and transition electron microscopic observations.     

A macaroni-like Li1.2V3O8 nanomaterial with high capacity for aqueous rechargeable lithium batteries

A macaroni-like Li_1.2V₃O₈ nanomaterial was directly prepared through a facile solution route using β-cyclodextrin (β-CD) as a template reagent. Its crystal structure was determined by the X-ray diffraction (XRD) pattern. From the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) micrographs, we observed that the as-prepared Li_1.2V₃O₈ material consisted of the aggregated macaroni-like nanoparticles and showed a porous structure. The electrochemical properties of the as-prepared Li_1.2V₃O₈ in 1.0 M Li₂SO₄ aqueous electrolyte were studied through cyclic voltammograms and charge-discharge measurements. The results revealed that the as-prepared Li_1.2V₃O₈ could deliver the initial specific capacities of 189, 140, and 101 mAh g⁻¹ at 0.1, 0.5, and 1.0 C, respectively. It suggests that the as-prepared Li_1.2V₃O₈ should have an attractive future to be applied in aqueous rechargeable lithium battery (ARLB).     

Mn3O4 nanoparticles embedded into graphene nanosheets: Preparation, characterization, and electrochemical properties for supercapacitors

Mn₃O₄/graphene nanocomposites were synthesized by mixing graphene suspension in ethylene glycol with MnO₂ organosol, followed by subsequent ultrasonication processing and heat treatment. The as-prepared product consists of nanosized Mn₃O₄ particles homogeneously distributed on graphene nanosheets, which has been confirmed by field emission scanning electron microscopy and transmission electron microscopy analysis. Atomic force microscope analysis further identified the distribution of dense Mn₃O₄ nanoparticles on graphene nanosheets. When used as electrode materials in supercapacitors, Mn₃O₄/graphene nanocomposites exhibited a high specific capacitance of 175 F g⁻¹ in 1 M Na₂SO₄ electrolyte and 256 F g⁻¹ in 6 M KOH electrolyte, respectively. The enhanced supercapacitance of Mn₃O₄/graphene nanocomposites could be ascribed to both electrochemical contributions of Mn₃O₄ nanoparticles, functional groups attached to graphene nanosheets, and significantly increased specific surface area.     

Enhanced electrochemical performances of LiNi0.5Mn1.5O4 spinel via ethylene glycol-assisted synthesis

A simple and effective method, ethylene glycol-assisted co-precipitation method, has been employed to synthesize LiNi_0.5Mn_1.5O₄ spinel. As a chelating agent, ethylene glycol can realize the homogenous distributions of metal ions at the atomic scale and prevent the growth of LiNi_0.5Mn_1.5O₄ particles. XRD reveals that the prepared material is a pure-phase cubic spinel structure (Fd3m) without any impurities. SEM images show that it has an agglomerate structure with the primary particle size of less than 100 nm. Electrochemical tests demonstrate that the as-prepared LiNi_0.5Mn_1.5O₄ possesses high capacity and excellent rate capability. At 0.1 C rate, it shows a discharge capacity of 137 mAh g⁻¹ which is about 93.4% of the theoretical capacity (146.7 mAh g⁻¹). At the high rate of 5 C, it can still deliver a discharge capacity of 117 mAh g⁻¹ with excellent capacity retention rate of more than 95% after 50 cycles. These results show that the as-prepared LiNi_0.5Mn_1.5O₄ is a promising cathode material for high power Li-ion batteries.     

Controllable synthesis of CaTi2O4(OH)2 nanoflakes by a facile template-free process and its properties

Serrated leaf-like CaTi₂O₄(OH)₂ nanoflake crystals were synthesized via a template-free and surfactant-free hydrothermal process. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The growth process for CaTi₂O₄(OH)₂ nanoflakes was dominated by a crystallization–dissolution–recrystallization growth mechanism. BET analysis showed that CaTi₂O₄(OH)₂ nanoflakes had mesoporous structure with an average pore size of 8.7 nm, and a large surface area of 88.4 m² g⁻¹. Cyclic voltammetry and galvanostatic charge–discharge tests revealed that the electrode synthesized from CaTi₂O₄(OH)₂ nanoflakes reached specific capacitances of 162 F g⁻¹ at the discharge current of 2 mA cm⁻², and also exhibited excellent electrochemical stability.     

Electrochemical performance of single crystalline spinel LiMn2O4 nanowires in an aqueous LiNO3 solution

Single crystalline cubic spinel LiMn₂O₄ nanowires were synthesized by hydrothermal method and the precursor calcinations. The phase structures and morphologies were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). Galvanostatic charging/discharging cycles of as-prepared LiMn₂O₄ nanowires were performed in an aqueous LiNO₃ solution. The initial discharge capacity of LiMn₂O₄ nanowires was 110 mAh g⁻¹, and the discharge capacity was still above 100 mAh g⁻¹ after 56 cycles at 10C-rate, and then 72 mAh g⁻¹ was registered after 130 cycles. This is the first report of a successful use of single crystalline spinel LiMn₂O₄ nanowire as cathode material for the aqueous rechargeable lithium battery (ARLB).     

Rapid microwave-assisted synthesis of graphene nanosheet/Co3O4 composite for supercapacitors

Graphene nanosheet (GNS)/Co₃O₄ composite has been rapidly synthesized by microwave-assisted method. Field emission scanning electron microscopy and transmission electron microscopy observation reveals the homogeneous distribution of Co₃O₄ nanoparticles (3-5 nm in size) on graphene sheets. Electrochemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. A maximum specific capacitance of 243.2 F g⁻¹ has been obtained at a scan rate of 10 mV s⁻¹ in 6 M KOH aqueous solution for GNS/Co₃O₄ composite. Furthermore, the composite exhibits excellent long cycle life along with ∼95.6% specific capacitance retained after 2000 cycle tests.     

Preparation and characterization of three dimensionally ordered macroporous Li4Ti5O12 anode for lithium batteries

Three dimensionally ordered macroporous (3DOM) Li₄Ti₅O₁₂ membrane (80 μm thick) was prepared by a colloidal crystal templating process. Colloidal crystal consisting of monodisperse polystyrene particles (1 μm diameter) was used as the template for the preparation of macroporous Li₄Ti₅O₁₂. A precursor sol consisting of titanium isopropoxide and lithium acetate was impregnated into the void space of template, and it was calcined at various temperatures. A macroporous membrane of Li₄Ti₅O₁₂ with inverse-opal structure was successfully prepared at 800 °C. The interconnected pores with uniform size (0.8 μm) were clearly observed on the entire part of membrane. The electrochemical properties of the three dimensionally ordered Li₄Ti₅O₁₂ were characterized with cyclic voltammetry and galvanostatic charge and discharge in an organic electrolyte containing a lithium salt. The 3DOM Li₄Ti₅O₁₂ exhibited a discharge capacity of 160 mA h g⁻¹ at the electrode potential of 1.55 V versus Li/Li⁺ due to the solid state redox of Ti^3+/4+ accompanying with Li⁺ ion insertion and extraction. The discharge capacity was close to the theoretical capacity (167 mA h g⁻¹), which suggested that the Li⁺ ion insertion and extraction took place at the entire part of 3DOM Li₄Ti₅O₁₂ membrane. The 3DOM Li₄Ti₅O₁₂ electrode showed good cycle stability.     

All-solid-state lithium battery with a three-dimensionally ordered Li1.5Al0.5Ti1.5(PO4)3 electrode

To fabricate all-solid-state Li batteries using three-dimensionally ordered macroporous Li_1.5Al_0.5Ti_1.5(PO₄)₃ (3DOM LATP) electrodes, the compatibilities of two anode materials (Li₄Mn₅O₁₂ and Li₄Ti₅O₁₂) with a LATP solid electrolyte were tested. Pure Li₄Ti₅O₁₂ with high crystallinity was not obtained because of the formation of a TiO₂ impurity phase. Li₄Mn₅O₁₂ with high crystallinity was produced without an impurity phase, suggesting that Li₄Mn₅O₁₂ is a better anode material for the LATP system. A Li₄Mn₅O₁₂/3DOM LATP composite anode was fabricated by the colloidal crystal templating method and a sol-gel process. Reversible Li insertion into the fabricated Li₄Mn₅O₁₂/3DOM LATP anode was observed, and its discharge capacity was measured to be 27 mA h g⁻¹. An all-solid-state battery composed of LiMn₂O₄/3DOM LATP cathode, Li₄Mn₅O₁₂/3DOM LATP anode, and a polymer electrolyte was fabricated and shown to operate successfully. It had a potential plateau that corresponds to the potential difference expected from the intrinsic redox potentials of LiMn₂O₄ and Li₄Mn₅O₁₂. The discharge capacity of the all-solid-state battery was 480 μA h cm⁻².     

Structural and magnetic properties of Co1−xZnxFe2O4 nanorods prepared by the solvothermal annealing method

Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods have been prepared by the thermal decomposition of the corresponding oxalate precursor, which was synthesized by the template-, surfactant-free solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM). The obtained Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods were built by many nanoparticles with average sizes around 20 nm to form one-dimensional arrays. Vibrating sample magnetometry measurements show that the coercivity of the ferrite nanorods decreases with increasing Zn content, whereas the specific saturation magnetization initially increases and then decreases with the increase of Zn content. The maximum saturation magnetization value of the as-prepared sample (Co_0.5Zn_0.5Fe₂O₄) reaches 43.0 emu g⁻¹.     

Enhanced cycling performance of Fe3O4-graphene nanocomposite as an anode material for lithium-ion batteries

Fe₃O₄-graphene nanocomposite was prepared by a gas/liquid interface reaction. The structure and morphology of the Fe₃O₄-graphene nanocomposite were characterized by X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. The electrochemical performances were evaluated in coin-type cells. Electrochemical tests show that the Fe₃O₄-22.7 wt.% graphene nanocomposite exhibits much higher capacity retention with a large reversible specific capacity of 1048 mAh g⁻¹ (99% of the initial reversible specific capacity) at the 90th cycle in comparison with that of the bare Fe₃O₄ nanoparticles (only 226 mAh g⁻¹ at the 34th cycle). The enhanced cycling performance can be attributed to the facts that the graphene sheets distributed between the Fe₃O₄ nanoparticles can prevent the aggregation of the Fe₃O₄ nanoparticles, and the Fe₃O₄-graphene nanocomposite can provide buffering spaces against the volume changes of Fe₃O₄ nanoparticles during electrochemical cycling.     

Hydrothermal synthesis of layered Li[Ni1/3Co1/3Mn1/3]O2 as positive electrode material for lithium secondary battery

In attempts to prepare layered Li[Ni_1/3Co_1/3Mn_1/3]O₂, hydrothermal method was employed. The hydrothermal precursor, [Ni_1/3Co_1/3Mn_1/3](OH)₂, was synthesized via a coprecipitation route. The sphere-shaped powder precursor was hydrothermally reacted with LiOH aqueous solution at 170 °C for 4 days in autoclave. From X-ray diffraction and scanning electron microscopic studies, it was found that the as-hydrothermally prepared powders were crystallized to layered α-NaFeO₂ structure and the particles had spherical shape. The as-prepared Li[Ni_1/3Co_1/3Mn_1/3]O₂ delivered an initial discharge of about 110 mA h g⁻¹ due to lower crystallinity. Heat treatment of the hydrothermal product at 800 °C was significantly effective to improve the structural integrity, which consequently affected the increase in the discharge capacity to 157 (4.3 V cut-off) and 182 mA h g⁻¹ (4.6 V cut-off) at 25 °C with good reversibility.     

Spray-drying synthesized LiNi0.6Co0.2Mn0.2O2 and its electrochemical performance as cathode materials for lithium ion batteries

Layered LiNi_0.6Co_0.2Mn_0.2O₂ materials were synthesized at different sintering temperatures using spray-drying precursor with molar ratio of Li/Me = 1.04 (Me = transition metals). The influences of sintering temperature on crystal structure, morphology and electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and charge-discharge test. As a result, material synthesized at 850 °C has excellent electrochemical performance, delivering an initial discharge capacity of 173.1 mAh g^− 1 between 2.8 and 4.3 V at a current density of 16 mA g^− 1 and exhibiting good cycling performance.     

Electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material synthesized by a sol-gel method

A carbon coated Li₃V₂(PO₄)₃ cathode material for lithium ion batteries was synthesized by a sol-gel method using V₂O₅, H₂O₂, NH₄H₂PO₄, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P2₁/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li₃V₂(PO₄)₃ electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g⁻¹ was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). It was found that the increase in total carbon content can improve the discharge performance of the Li₃V₂(PO₄)₃ electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li₃V₂(PO₄)₃ host are almost reversible, exhibiting a reversible capacity of 177 mAh g⁻¹ and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ cathode material were also discussed.     

A perovskite-type KNbO3 nanoneedles based biosensor for direct electrochemistry of hydrogen peroxide

A KNbO₃ nanoneedles (KNs) based hydrogen peroxide (H₂O₂) biosensor was first proposed. Perovskite-type KNs can directly catalyze H₂O₂. The mechanism can be explained by Molecular Orbital Principles, with the formation of σ-bonding between the e_g orbital of surface niobium ions and surface adsorbed oxygen-related intermediate species. Direct electron transfer between the Horseradish peroxidase (HRP) and electrode surface was achieved. Co-catalyst system of both HRP and KNbO₃ was introduced to the oxidation of H₂O₂, thus the as-prepared biosensor exhibited high sensitivity (750 μA mM⁻¹ cm⁻²) and ultrafast response (1–2 s) to H₂O₂. Therefore, KNs provide a promising material for enzymes assembly and sensing application.     

A designed Mn2O3/MCM-41 nanoporous composite for methylene blue and rhodamine B removal with high efficiency

The authors report a facile chemical precipitation method for the fabrication of a highly ordered mesoporous Mn₂O₃/MCM-41 composite. Examination of the acquired samples using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption measurement has provided fundamental insight into the structure and properties of the Mn₂O₃/MCM-41 composite. It is found that the as-prepared Mn₂O₃/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 793 m² g⁻¹. The performance of Mn₂O₃/MCM-41 composite as a remover was further demonstrated in the removal of azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB), and rhodamine B (RB) with/without visible light irradiation at room temperature. The results show that the Mn₂O₃/MCM-41 composite has an excellent removal performance for MB and RB, making it a promising candidate for wastewater treatment.     

Hydrothermal synthesis of flower-like Zn2SnO4 composites and their performance as anode materials for lithium-ion batteries

Flower-like Zn₂SnO₄ composites had been prepared through a green hydrothermal synthesis. The structural, morphological and electrochemical properties were investigated by means of XRD, BET, SEM, TEM, and electrochemical measurement. The results show that the as-prepared sample is in high purity phase and of good crystallinity; meanwhile it has a particular 3-D structure and large surface area. Electrochemical measurement suggests that flower-like Zn₂SnO₄ composites exhibit better cycling properties and lower initial irreversible capacities than the solid Zn₂SnO₄ cubes. The first discharge and charge capacities of the material are 1750 mA h g⁻¹ and 880 mA h g⁻¹ respectively. A higher reversible capacity of 501 mA h g⁻¹ was obtained after 50 cycles at a current density of 300 mA g⁻¹. The higher reversible capacity and good stability can be related to the special nanostructural features of the material. Such Zn₂SnO₄ structures synthesized by the simple and cheap method are expected to have potential application in energy storage.     

Rheological phase reaction synthesis and electrochemical performance of Li3V2(PO4)3/carbon cathode for lithium ion batteries

Monoclinic lithium vanadium phosphate/carbon (Li₃V₂(PO₄)₃/C) cathode has been synthesized for applications in lithium ion batteries, via a rheological phase reaction (RPR) method. The sample is characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). This material exhibits high initial discharge capacity of 189 and 177 mAh g⁻¹ at 0.1 and 0.2 C between 3.0 and 4.8 V, respectively. Moreover, it displays good fast rate performance, which discharge capacities of 140, 133, 129 and 124 mAh g⁻¹ can be delivered after 100 cycles between 3.0 and 4.8 V vs. Li at a different rate of 0.5, 1, 2 and 5 C, respectively. The electrochemical impedance spectroscopy (EIS) is also investigated.     

Synthesis and characterization of high-density non-spherical Li(Ni1/3Co1/3Mn1/3)O2 cathode material for lithium ion batteries by two-step drying method

Non-spherical Li(Ni_1/3Co_1/3Mn_1/3)O₂ powders have been synthesized using a two-step drying method with 5% excess LiOH at 800 °C for 20 h. The tap-density of the powder obtained is 2.95 g cm⁻³. This value is remarkably higher than that of the Li(Ni_1/3Co_1/3Mn_1/3)O₂ powders obtained by other methods, which range from 1.50 g cm⁻³ to 2.40 g cm⁻³. The precursor and Li(Ni_1/3Co_1/3Mn_1/3)O₂ are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the precursor are 2⁺, 3⁺ and 4⁺, respectively. XRD results show that the Li(Ni_1/3Co_1/3Mn_1/3)O₂ material obtained by the two-step drying method has a well-layered structure with a small amount of cation mixing. SEM confirms that the Li(Ni_1/3Co_1/3Mn_1/3)O₂ particles obtained by this method are uniform. The initial discharge capacity of 167 mAh g⁻¹ is obtained between 3 V and 4.3 V at a current of 0.2 C rate. The capacity of 159 mAh g⁻¹ is retained at the end of 30 charge-discharge cycle with a capacity retention of 95%.     

Rapid preparation and electrochemical behavior of carbon-coated Li3V2(PO4)3 from wet coordination

An improved solid-state coordination method namely wet coordination has been developed to synthesize carbon-coated monoclinic Li₃V₂(PO₄)₃ rapidly at a low temperature of 600 °C in 1 h. The structure of the sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and energy dispersive analysis of X-rays (EDAX). The diffusion coefficient of the lithium ions was measured by cyclic voltammetry (CV). The electrochemical behavior of the sample exhibits a high initial discharge capacity of 130 mAh g⁻¹, which is very close to its theoretical capacity of 132 mAh g⁻¹ under 95 mA g⁻¹ (0.67 C) in the range of 3.3-4.3 V (vs. Li/Li⁺). These results suggest that wet coordination is a promising method for large-scale production of carbon-coated Li₃V₂(PO₄)₃.