Electrochemical properties of facile emulsified LiV3O8 materials

LiV₃O₈ cathode materials are post-treated by a special emulsion method (termed “EM”) and then calcinated at different temperatures. The experimental results show that the structure of these oxides is different from LiV₃O₈ prepared by the solid-state reaction (acronym “STATE”) route, although their starting materials are identical. The EM product prepared at 500 °C exhibits a better electrochemical behavior than its counterpart prepared by traditional methods (STATE) or by EM at other temperatures. Its initial discharge capacity is 305 mAh g⁻¹, and it still maintains 250.2 mAh g⁻¹ after 100 cycles at 0.2 C at the voltage range of 1.8–4.0 V vs. Li/Li⁺.     

Preparation and electrochemical properties of Cr doped LiV3O8 cathode for lithium ion batteries

Chromium was incorporated into lithium trivanadate by an aqueous reaction followed by heating at 100 °C. This Cr doped LiV₃O₈ as a cathode for lithium ion batteries exhibits 269.9 mAh g^− 1 at first discharge cycle and remains 254.8 mAh g^− 1 at cycle 100, with a charge-discharge current density of 150 mA g^− 1 in the voltage range of 1.8-4.0 V. The Cr-LiV₃O₈ cathode show excellent discharge capacity, with the retention of 94.4% after 100 cycles. These result values are higher than previous reports indicating that Cr-LiV₃O₈ prepared by our low temperature synthesis method is a promising cathode material for rechargeable lithium ion batteries. The enhanced discharge capacity and cycle stability of Cr-LiV₃O₈ cathode indicate that chromium atoms promote lithium transfer or intercalation/deintercalation during the electrochemical cycles and improve the electrochemical performances of LiV₃O₈ cathode.     

CTAB-assisted sol-gel synthesis of Li4Ti5O12 and its performance as anode material for Li-ion batteries

A simple CTAB-assisted sol-gel technique for synthesizing nano-sized Li₄Ti₅O₁₂ with promising electrochemical performance as anode material for lithium ion battery is reported. The structural and morphological properties are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical performance of both samples (with and without CTAB) calcined at 800 °C is evaluated using Swagelok™ cells by galvanostatic charge/discharge cycling at room temperature. The XRD pattern for sample prepared in presence of CTAB and calcined at 800 °C shows high-purity cubic-spinel Li₄Ti₅O₁₂ phase (JCPDS # 26-1198). Nanosized-Li₄Ti₅O₁₂ calcined at 800 °C in presence of CTAB exhibits promising cycling performance with initial discharge capacity of 174 mAh g⁻¹ (∼100% of theoretical capacity) and sustains a capacity value of 164 mAh g⁻¹ beyond 30 cycles. By contrast, the sample prepared in absence of CTAB under identical reaction conditions exhibits initial discharge capacity of 140 mAh g⁻¹ (80% of theoretical capacity) that fades to 110 mAh g⁻¹ after 30 cycles.     

Effect of Co0.58Ni0.42 oxide nanoneedles coating on the electrochemical properties of LiV3O8 cathode

LiV₃O₈ has been coated by various amounts of Co_0.58Ni_0.42 oxide nanoneedles using a chemical co-precipitation method. The influences of the coating on the structure, morphology, and electrochemical properties of LiV₃O₈ have been characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), and electrochemical measurements. Co_0.58Ni_0.42 oxide coated LiV₃O₈ materials exhibit distinct surface morphology. The coating has been found to improve the electrochemical performance of LiV₃O₈ significantly. Especially, 5.0 wt.% Co_0.58Ni_0.42 oxide nanoneedles coated LiV₃O₈ shows much better electrochemical performance than uncoated LiV₃O₈. It has been proved that Co_0.58Ni_0.42 oxide coating suppresses phase transitions and decreases the charge-transfer impedance of LiV₃O₈ effectively.     

Preparation of LiFePO4/C composite powders by ultrasonic spray pyrolysis followed by heat treatment and their electrochemical properties

LiFePO₄ powders could be successfully prepared from a precursor solution, which was composed of Li(HCOO)·H₂O, FeCl₂·4H₂O and H₃PO₄ stoichiometrically dissolved in distilled water, by ultrasonic spray pyrolysis at 500 °C followed by heat treatment at sintering temperatures ranging from 500 to 800 °C in N₂ + 3% H₂ gas atmosphere. Raman spectroscopy revealed that α-Fe₂O₃ thin layers were formed on the surface of as-prepared LiFePO₄ powders during spray pyrolysis, and they disappeared after sintering above 600 °C. The LiFePO₄ powders prepared at 500 °C and then sintered at 600 °C exhibited a first discharge capacity of 100 mAh g⁻¹ at a 0.1 C charge-discharge rate. To improve the electrochemical properties of the LiFePO₄ powders, LiFePO₄/C composite powders with various amounts of citric acid added were prepared by the present method. The LiFePO₄/C (1.87 wt.%) composite powders prepared at 500 °C and then sintered at 800 °C exhibited first-discharge capacities of 140 mAh g⁻¹ at 0.1 C and 84 mAh g⁻¹ at 5 C with excellent cycle performance. In this study, the optimum amount of carbon for the LiFePO₄/C composite powders was 1.87 wt.%. From the cyclic voltammetry (CV) and AC impedance spectroscopy measurements, the effects of carbon addition on the electrochemical properties of LiFePO₄ powders were also discussed.     

Low temperature synthesis of Fe3O4 nanoparticles and its application in lithium ion batteries

Well dispersed Fe₃O₄ nanoparticles with mean size about 160 nm are synthesized by a simple chemical method at atmosphere pressure. The products are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and Raman spectrum. Electrochemical properties of the as-synthesized Fe₃O₄ nanoparticles as anode electrodes of lithium ion batteries are studied by conventional charge/discharge tests, showing initial discharge and charge capacities of 1140 mAh g⁻¹ and 1038 mAh g⁻¹ at a current density of 0.1 mA cm⁻². The charge and discharge capacities of Fe₃O₄ electrode decrease along with the increase of cycle number, arriving at minimum values near the 70th cycle. After that, the discharge and charge capacities of Fe₃O₄ electrode begin to increase along with the increase of cycle number, arriving at 791 and 799 mAh g⁻¹ after 393 cycles. The morphology and size of the electrode after charge and discharge tests are characterized by SEM, which exhibits a large number of dispersive particles with mean size about 150 nm.     

High rate performance of novel cathode material Li1.33Ni1/3Co1/3Mn1/3O2 for lithium ion batteries

Li_1.33Ni_1/3Co_1/3Mn_1/3O₂ with highly ordered structure has been successfully synthesized via a simple co-precipitation process. Charge–discharge tests showed that the initial discharge capacities are 153.0 mAh g⁻¹ and 128.9 mAh g⁻¹ at 5 C (1000 mA g⁻¹) and 10 C (2000 mA g⁻¹) between 2.5 and 4.5 V, respectively. The average full-charge time of this material is less than 12 min at 5 C and 6 min at 10 C. The electrode material composed of the prepared showed a better cyclability. The excellent high rate performance is attributed to the improved ordered layered structure and the electrical conductivity. The excess Li shorten Li⁺ diffusion distance between these submicron and nano-scaled particles. The results show that Li_1.33Ni_1/3Co_1/3Mn_1/3O₂ cathode material has potential application in lithium ion batteries.     

One-pot syntheses of Li3V2(PO4)3/C cathode material for lithium ion batteries via ascorbic acid reduction approach

Monoclinic Li₃V₂(PO₄)₃/C composite synthesized by ascorbic acid reduction method is examined as a cathode material for Li-ion batteries. Transmission electron microscopy (TEM) images show that the nano-size particles are obtained. The reversible capacity of Li₃V₂(PO₄)₃/C prepared with LiOH and H₃PO₄ is 141.2 mAh g⁻¹ after 100 cycles at 1C discharge rate between 3 V and 4.8 V, and the retention rates of discharge capacity is 93.4%. Ascorbic acid plays not only as reduction reagent, but also as carbon sources. This strategy shortens the time of solid state reaction and facilitates the procedure of synthesis. Effects of different precursors materials on the performance of the Li₃V₂(PO₄)₃/C are investigated.     

Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy

SiO₂/Al₂O₃ composite microspheres with SiO₂ core/Al₂O₃ shell structure and high surface area were prepared by depositing Al₂O₃ colloid particles on the surface of monodispersed microporous silica microspheres using a simple electrostatic attraction and heterogeneous nucleation strategy, and then calcined at 600 °C for 4 h. The prepared products were characterized with differential thermal analysis and thermogravimetric analysis (DTA/TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It was found that uniform alumina coating could be deposited on the surface of silica microspheres by adjusting the pH values of the reaction solution to an optimal pH value of about 6.0. The specific surface area and pore volume of the SiO₂/Al₂O₃ composite microspheres calcined at 600 °C were 653 m² g⁻¹ and 0.34 ml g⁻¹, respectively.     

The effects of quenching treatment and AlF3 coating on LiNi0.5Mn0.5O2 cathode materials for lithium-ion battery

Submicron layered LiNi_0.5Mn_0.5O₂ was synthesized via a co-precipitation and solid-state reaction method together with a quenching process. The crystal structure and morphology of the materials were investigated by X-ray diffraction (XRD), Brunauer–Emmett and Teller (BET) surface area and scanning electron microscopy (SEM) techniques. It is found that LiNi_0.5Mn_0.5O₂ material prepared with quenching methods has smooth and regular structure in submicron scale with surface area of 0.43 m² g⁻¹. The initial discharge capacities are 175.8 mAh g⁻¹ at 0.1 C (28 mA g⁻¹) and 120.3 mAh g⁻¹ at 5.0 C (1400 mA g⁻¹), respectively, for the quenched samples between 2.5 and 4.5 V. It is demonstrated that quenching method is a useful approach for the preparation of submicron layered LiNi_0.5Mn_0.5O₂ cathode materials with excellent rate performance. In addition, the cycling performance of quenched-LiNi_0.5Mn_0.5O₂ material was also greatly improved by AlF₃ coating technique.     

High capacity and good cycling stability of multi-walled carbon nanotube/SnO2 core-shell structures as anode materials of lithium-ion batteries

The multi-walled carbon nanotube/SnO₂ core-shell structures were fabricated by a wet chemical route. The electrochemical performance of the core-shell structures as anode materials of lithium-ion batteries was investigated. The initial discharge capacity and reversible capacity are up to 1472.7 and 1020.5 mAh g⁻¹, respectively. Moreover, the reversible capacity still remains above 720 mAh g⁻¹ over 35 cycles, and the capacity fading is only 0.8% per cycle. Such high capacities and good cyclability are attributed to SnO₂ network structures, excellent mechanical property and good electrical conductivity of the multi-walled carbon nanotubes.     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.     

Synthesis of spherical LiMnPO4/C composite microparticles

Spherical LiMnPO₄/C composite microparticles were prepared by a combination of spray pyrolysis and spray drying followed by heat treatment and examined as a cathode material for lithium batteries. The structure, morphology and electrochemical performance of the resulting spherical LiMnPO₄/C microparticles were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electronic microscopy and standard electrochemical techniques. The final sample was identified as a single phase orthorhombic structure of LiMnPO₄ and spherical powders with a geometric mean diameter of 3.65 μm and a geometric standard deviation of 1.34. The electrochemical cells contained the spherical LiMnPO₄/C microparticles exhibited first discharge capacities of 112 and 130 mAh g⁻¹ at 0.05 C at room temperature and 55 °C, respectively. These also showed a good rate capability up to 5 C at room temperature and 55 °C.     

Nano-sized Li-Fe composite oxide prepared by a self-catalytic reverse atom transfer radical polymerization approach as an anode material for lithium-ion batteries

A novel Self-catalytic Reverse Atom Transfer Radical Polymerization (RATRP) approach that can provide the radical initiator and the catalyst by the system itself is used to synthesize a nano-sized Li-Fe composite oxide powder in large scale. Its crystalline structure and morphology have been characterized by X-ray diffraction and scanning electron microscopy. The results reveal that the composite is composed of nano-sized LiFeO₂ and Fe₃O₄. Its electrochemical properties are evaluated by charge/discharge measurements. The results show that the Li-Fe composite oxide is an excellent anode material for lithium-ion batteries with good cycling performance (1249 mAh g⁻¹ at 100th cycle) and outstanding rate capability (967 mAh g⁻¹ at 5 C). Such a self-catalytic RATRP approach provides a way to synthesize nano-sized iron oxide-based anode materials industrially with preferable electrochemical performance and can also be applied in other polymer-related area.     

Microporous carbon derived from polyaniline base as anode material for lithium ion secondary battery

Microporous carbon with large surface area was prepared from polyaniline base using K₂CO₃ as an activating agent. The physicochemical properties of the carbon were characterized by scanning electron microscope, X-ray diffraction, Brunauer-Emmett-Teller, elemental analyses and X-ray photoelectron spectroscopy measurement. The electrochemical properties of the microporous carbon as anode material in lithium ion secondary battery were evaluated. The first discharge capacity of the microporous carbon was 1108 mAh g⁻¹, whose first charge capacity was 624 mAh g⁻¹, with a coulombic efficiency of 56.3%. After 20 cycling tests, the microporous carbon retains a reversible capacity of 603 mAh g⁻¹ at a current density of 100 mA g⁻¹. These results clearly demonstrated the potential role of microporous carbon as anode for high capacity lithium ion secondary battery.     

Preparation and electrochemical performance of LiFePO4/C composite with network connections of nano-carbon wires

LiFePO₄/C composite with network connections of nano-carbon wires was successfully prepared by using polyvinyl alcohol as carbon source. The composite was characterized by X-ray diffraction and transmission electron microscopic, and its electrochemical performance was investigated by galvanostatic charge and discharge tests. The experimental results show that LiFePO₄ grains are tightly connected by the network of nano-carbon wires. Moreover LiFePO₄/C composite exhibits high capacity of 168 mAh g⁻¹ applied 15 mA g⁻¹ current density (C/10), excellent cyclic ability and rate capability. When 1500 mA g⁻¹ current density (10C) was applied, the high discharge capacity of 129 mAh g⁻¹ has been obtained at room temperature.     

Synthesis of FePO4 cathode material for lithium ion batteries by a sonochemical method

Hydrated amorphous FePO₄ was synthesized by a sonochemical reaction method, in which a solution of (NH₄)₂HPO₄ and FeSO₄·7H₂O was irradiated by an ultrasonic wave. From this material, two kinds of cathode materials were easily prepared: (1) an amorphous sample prepared by heating at 350 °C and (2) a crystalline sample prepared by heating at 700 °C. Both samples consisted of homogeneous sub-micron particles. The amorphous sample of FePO₄ exhibited high discharge capacities with more than 100 mAh g⁻¹ in the range of 3.9-2.0 V versus Li/Li⁺ at a current rate of 0.2 C. The sonochemical synthesis proposed herein has the following advantages: no use of oxidation agents for production of trivalent iron ions, reduction in reaction time, control of particle size, and enlargement in surface area for the preparation of the cathode material.     

Synthesis and performance of LiMn0.7Fe0.3PO4 cathode material for lithium ion batteries

Pure and carbon-containing olivine LiMn_0.7Fe_0.3O₄ were synthesized at 600 °C by the method of solid-state reaction. Structure, surface morphology and charge/discharge performance of LiMn_0.7Fe_0.3O₄ were characterized by X-ray diffraction, scanning electron microscopy, and electrochemical measurement, respectively. The prepared materials with and without carbon both show the single olivine structure. The morphologies of primary particles are greatly affected by the addition of carbon. Large particles (500-1000 nm) and densely sintered blocks were observed in pure LiMn_0.7Fe_0.3PO₄, which made the insertion and extraction of lithium ions difficult. Battery made from this sample can not charge and discharge effectively. The carbon-containing LiMn_0.7Fe_0.3PO₄ has a small particle size (100-200 nm) and a regular appearance. This material demonstrates high reversible capacity of about 120 mAh g⁻¹, perfect cycling performance, and excellent rate capability. It is obvious that the addition of carbon plays an important role in restricting the particle size of the material, which helps to prepare LiMn_0.7Fe_0.3PO₄ with excellent electrochemical performance. The electrochemical reaction resistance is much lower in the partly discharged state than in the fully charged or fully discharged state by the measurement of ac impedance for carbon-containing LiMn_0.7Fe_0.3PO₄. It is indicated that the mixed-valence of Fe³⁺/Fe²⁺ or Mn³⁺/Mn²⁺ is beneficial to the transfer of electron which happens between the interface.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.     

Organic phosphoric sources for syntheses of Li3V2(PO4)3/C via improved rheological phase reaction

Li₃V₂(PO₄)₃/C is synthesized by an improved rheological phase method using Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) as organic phosphoric sources. The phosphoric sources with carbon chains can inhibit the grain growth of Li₃V₂(PO₄)₃ particles. X-ray powder diffraction pattern shows that the obtained Li₃V₂(PO₄)₃/C sample is monoclinic phase. Transmission electron microscope results show that the thickness of carbon layer is about 10 nm. The form of residual carbon is confirmed by Raman spectroscopy. The Li₃V₂(PO₄)₃/C sample prepared by 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) displays the initial discharge capacity of 158 mAh g^− 1 and keeps 130 mAh g^− 1 after 100 cycles at 1 C rate. The improved rheological phase reaction method can be used for synthesis of Li₃V₂(PO₄)₃ cathode material and other polyanion materials.