Synthesis of spinel LiMn2O4 with manganese carbonate prepared by micro-emulsion method

Micro-spherical particle of MnCO₃ has been successfully synthesized in CTAB-C₈H₁₈-C₄H₉OH-H₂O micro-emulsion system. Mn₂O₃ decomposed from the MnCO₃ is mixed with Li₂CO₃ and sintered at 800 °C for 12 h, and the pure spinel LiMn₂O₄ in sub-micrometer size is obtained. The LiMn₂O₄ has initial discharge specific capacity of 124 mAh g⁻¹ at discharge current of 120 mA g⁻¹ between 3 and 4.2 V, and retains 118 mAh g⁻¹ after 110 cycles. High-rate capability test shows that even at a current density of 16 C, capacity about 103 mAh g⁻¹ is delivered, whose power is 57 times of that at 0.2 C. The capacity loss rate at 55 °C is 0.27% per cycle.     

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

To achieve a high-energy-density lithium electrode, high-density LiFePO₄/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO₄ as a precursor, glucose as a C source, and Li₂CO₃ as a Li source, in a pipe furnace under an atmosphere of 5% H₂-95% N₂. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO₄/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO₄/carbon composite powder with a carbon content of 7% reached 1.80 g m⁻³. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g⁻¹, respectively, with a volume capacity of 300.6 mAh cm⁻³, at a 0.1C rate. At a rate of 5C, the LiFePO₄/carbon composite shows a high discharge capacity of 98.3 mAh g⁻¹ and a volume capacity of 176.94 mAh cm⁻³.     

A novel micro-spherical CoSn2/Sn alloy composite as high capacity anode materials for Li-ion rechargeable batteries

Micro-scaled spherical CoSn₂/Sn alloy powders synthesized from oxides of Sn and Co via carbothermal reduction at 800 °C were examined for use as anode materials in Li-ion battery. The phase composition and particle morphology of the CoSn₂/Sn alloy composite powders were investigated by XRD, SEM and TEM. The prepared CoSn₂/Sn alloy composite electrode exhibits a low initial irreversible capacity of ca. 140 mAh g⁻¹, a high specific capacity of ca. 600 mAh g⁻¹ at constant current density of 50 mA g⁻¹, and a good rate capability. The stable discharge capacities of 500-515 mAh g⁻¹ and the columbic efficiencies of 95.8-98.1% were obtained at current density of 500 mA g⁻¹. The relatively large particle size of CoSn₂/Sn alloy composite powder is apparently favorable for the lowering of initial capacity loss of electrode, while the loose particle structural characteristic and the Co addition in Sn matrix should be responsible for the improvement of cycling stability of CoSn₂/Sn electrode.     

Enhanced electrochemical properties of LiFePO4/C synthesized with two kinds of carbon sources,PEG-4000 (organic) and Super p (inorganic)

Olivine structured LiFePO₄/C cathode was synthesized via a freeze-drying route and followed by microwave heating with two kinds of carbon sources: PEG-4000 (organic) and Super p (inorganic). XRD patterns indicate that the as-prepared sample has an olivine structure and carbon modification does not affect the structure of the sample. Image of SEM shows a uniform and optimized particles size, which greatly improves the electrochemical properties. TEM result reveals the amorphous carbon around the surface of the particles. At a low rate of 0.1 C, the LiFePO₄/C sample presents a high discharge capacity of 157.8 mAh g⁻¹ which is near the theoretical capacity (170 mAh g⁻¹), and it still attains to 149.1 mAh g⁻¹ after 200 cycles. It also exhibits an excellent rate capacity with high discharge capacities of 143.2 mAh g⁻¹, 137.5 mAh g⁻¹, 123.7 mAh g⁻¹ and 101.6 mAh g⁻¹ at 0.5 C, 1.0 C, 2.0 C and 5.0 C, respectively. EIS results indicate that the charge transfer resistance of LiFePO₄ decreases greatly after carbon coating.     

Synthesis and electrochemical performance of Li2FeSiO4/carbon/carbon nano-tubes for lithium ion battery

Li₂FeSiO₄/carbon/carbon nano-tubes (Li₂FeSiO₄/C/CNTs) and Li₂FeSiO₄/carbon (Li₂FeSiO₄/C) composites were synthesized by a traditional solid-state reaction method and characterized comparatively by X-ray diffraction, scanning electron microscopy, BET surface area measurement, galvanostatic charge-discharge and AC impedance spectroscopy, respectively. The results revealed that the Li₂FeSiO₄/C/CNT composite exhibited much better rate performance in comparison with the Li₂FeSiO₄/C composite. At 0.2 C, 5 C and 10 C, the former composite electrode delivered a discharge capacity of 142 mAh g⁻¹, 95 mAh g⁻¹, 80 mAh g⁻¹, respectively, and after 100 cycles at 1 C, the discharge capacity remained 95.1% of its initial value.     

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.     

LiFePO4 cathode power with high energy density synthesized by water quenching treatment

A water quenching (WQ) method was developed to synthesize LiFePO₄ and C-LiFePO₄. Our results indicate that this synthesis method ensures improved electrochemical activity and small crystal grain size. The synthetic conditions were optimized using orthogonal experiments. The LiFePO₄ sample prepared at the optimized condition showed a maximum discharge capacity of 149.8 mAh g⁻¹ at a C/10 rate. C-LiFePO₄ with a low carbon content of 0.93% and a high discharge specific capacity of 163.8 mAh g⁻¹ has also been obtained using this method. Water quenching treatment shows outstanding improvement of the electrochemical performance of LiFePO₄.     

Synthesis of highly crystalline spinel LiMn2O4 by a soft chemical route and its electrochemical performance

Highly crystalline spinel LiMn₂O₄ was successfully synthesized by annealing lithiated MnO₂ at a relative low temperature of 600 °C, in which the lithiated MnO₂ was prepared by chemical lithiation of the electrolytic manganese dioxide (EMD) and LiI. The LiI/MnO₂ ratio and the annealing temperature were optimized to obtain the pure phase LiMn₂O₄. With the LiI/MnO₂ molar ratio of 0.75, and annealing temperature of 600 °C, the resulting compounds showed a high initial discharge capacity of 127 mAh g⁻¹ at a current rate of 40 mAh g⁻¹. Moreover, it exhibited excellent cycling and high rate capability, maintaining 90% of its initial capacity after 100 charge-discharge cycles, at a discharge rate of 5 C, it kept more than 85% of the reversible capacity compared with that of 0.1 C.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

Effect of synthesis condition on the structural and electrochemical properties of Li[Ni1/3Mn1/3Co1/3]O2 prepared by the metal acetates decomposition method

In order to get homogeneous layered oxide Li[Ni_1/3Mn_1/3Co_1/3]O₂ as a lithium insertion positive electrode material, we applied the metal acetates decomposition method. The oxide compounds were calcined at various temperatures, which results in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni_1/3Mn_1/3Co_1/3]O₂ powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry and SEM. XRD experiment revealed that the layered Li[Ni_1/3Mn_1/3Co_1/3]O₂ material can be best synthesized at temperature of 800 °C. In that synthesized temperature, the sample showed high discharge capacity of 190 mAh g⁻¹ as well as stable cycling performance at a current density of 0.2 mA cm⁻² in the voltage range 2.3-4.6 V. The reversible capacity after 100 cycles is more than 190 mAh g⁻¹ at room temperature.     

Performance evaluation of printed LiCoO2 cathodes with PVDF-HFP gel electrolyte for lithium ion microbatteries

In order to improve the discharge capacity in lithium ion microbatteries, a thick-film cathode was fabricated by a screen printing using LiCoO₂ pastes. The printed cathode showed a different discharge curves when the cell was tested using various (liquid, gel and solid-state) electrolytes. When a cell test was performed with organic liquid electrolyte, the maximum discharge capacity was 200 μAh cm⁻², which corresponded to approximately 133 mAh g⁻¹ when the loading weight of LiCoO₂ was calculated. An all-solid-state microbattery could be assembled using sputtered LiPON electrolyte, an evaporated Li anode, and printed LiCoO₂ cathode films without delamination or electrical problems. However, the highest discharge capacity showed a very small value (7 μAh cm⁻²). This problem could be improved using a poly(vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) gel electrolyte, which enhanced the contact area and adhesion force between cathode and electrolyte. The discharge value of this cell was measured as approximately 164 μAh cm⁻² (≈110 mAh g⁻¹). As the PVDF-HFP electrolyte had a relatively soft contact property with higher ionic conductance, the cell performance was improved. In addition, the cell can be fabricated in a leakage-free process, which can resolve many safety problems. According to these results, there is a significant possibility that a film prepared using the aforementioned paste with screen printing and PVDF-HFP gel electrolyte is feasible for a microbattery.     

Molten salt synthesis of spherical LiNi0.5Mn1.5O4 cathode materials

This paper describes a novel simple redox process for synthesizing monodispersed MnO₂ powders and preparation of spherical LiNi_0.5Mn_1.5O₄ cathode materials by molten salt synthesis (MSS) method. Monodispersed MnO₂ powders have been synthesized by using potassium permanganate and manganese sulfate as the starting materials. By using this redox method, it was found that monodispersed MnO₂ powders with average particle size ∼5 μm can be easily obtained. Resultant MnO₂ and LiOH, Ni(OH)₂ was then used to synthesis LiNi_0.5Mn_1.5O₄ cathode materials with retention of spherical particle shape by MSS method. The discharge capacity was 129 mAh g⁻¹ in the first cycle and 127 mAh g⁻¹ after 50 cycles under an optimal synthesis condition for 12 h at 800 °C.     

Synthesis, characterization and electrochemical performance of mesoporous FePO4 as cathode material for rechargeable lithium batteries

Mesoporous FePO₄ could deliver enhanced specific capacity of 160 mAh g⁻¹ at first discharge process, 90% of theoretical capacity of pure FePO₄, and 135 mAh g⁻¹ in the following cycles at 0.1 C rate. At 1 and 3 C rates, the capacities are 110 and 85 mAh g⁻¹, respectively, which is much higher than that of previously reported for modified FePO₄ materials. Electrochemical impedance spectroscopy (EIS) tests proved that mesoporous structure in FePO₄ materials enhanced the lithium ion intercalation/deintercalation kinetics as indicated by smaller charge transfer resistance (R_ct) of these materials. These results revealed that this mesoporous electrode material can be a potential candidate for high-power energy conversion devices.     

Nonaqueous and template-free synthesis of Sb doped SnO2 microspheres and their application to lithium-ion battery anode

Antimony doped SnO₂ (ATO) microspheres composed of ATO nanoparticles were prepared by using a hydrothermal process in a nonaqueous and template-free solution from the inorganic precursors (SnCl₄ and Sb(OC₂H₅)₃). The physical properties of the as-synthesized samples were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption isotherms, and X-ray photoelectron spectrum (XPS). The resulting particles were highly crystalline ATO microspheres in the diameter range of 3-10 μm and with many pores. The as-prepared samples were used as negative materials for lithium-ion battery, whose charge-discharge properties, cyclic voltammetry, and cycle performance were examined. The results showed that a high initial discharge capacity of 1981 mAh g⁻¹ and a charge capacity of 957 mAh g⁻¹ in a potential range of 0.005-3.0 V was achieved, which suggests that tin oxide-based materials work as high capacity anodes for lithium-ion rechargeable batteries. The cycle performance is improved because the conducting ATO nanoparticles can also perform as a better matrix for lithium-ion battery anode.     

Polyvinylpyrrolidone-assisted synthesis of microscale C-LiFePO4 with high tap density as positive electrode materials for lithium batteries

Carbon-coated LiFePO₄ (C-LiFePO₄) with micron particle size (6 μm) and high tap density (1.6 g cm⁻³) was prepared from spherical FePO₄·2H₂O powder via the co-precipitation method. The C-LiFePO₄ powder was calcined at temperatures between 650 and 800 °C. The 6 μm C-LiFePO₄ prepared at 800 °C exhibited an excellent rate capability, delivering 150 mAh g⁻¹ on discharge at the 0.1 C-rate and 108 mAh g⁻¹ at the 5 C-rate. The volumetric capacity of the 6 μm C-LiFePO₄ corresponded to 225 mAh cm⁻³, since the large secondary particles (6 μm) C-LiFePO₄ sufficiently allowed tight packing of the particles. The 6 μm C-LiFePO₄ powder with high tap density makes an attractive positive electrode candidate for lithium-ion batteries designed for high energy density.     

One-step microwave synthesis and characterization of carbon-modified nanocrystalline LiFePO4

The precursors of LiFePO₄ were prepared by a sol-gel method using lithium acetate dihydrate, ferrous sulfate, phosphoric acid, citric acid and polyethylene glycol as raw materials, and then the carbon-modified nanocrystalline LiFePO₄ (LiFePO₄/C) cathode material was synthesized by a one-step microwave method with the domestic microwave oven. The effect of microwave time and carbon content on the performance of the resulting LiFePO₄/C material was investigated. Structural characterization by X-ray diffraction and scanning electron microscopy proved that the olivine phase LiFePO₄ was synthesized and the grain size of the samples was several hundred nanometers. Under the optimal conditions of microwave time and carbon content, the charge-discharge performance indicated that the nanosized LiFePO₄/C had a high electrochemical capacity at 0.2 C (152 mAh g⁻¹) and improved capacity retention; the exchange current density was 1.6977 mA cm⁻². Furthermore, the rate capability was improved effectively after LiFePO₄ was modified with carbon, with 59 mAh g⁻¹ being obtained at 20 C.     

Electrochemical performance of all-solid-state lithium secondary batteries with Li-Ni-Co-Mn oxide positive electrodes

LiNi_1/3Co_1/3Mn_1/3O₂ was applied as a promising material to the all-solid-state lithium cells using the 80Li₂S·19P₂S₅·1P₂O₅ (mol%) solid electrolyte. The cell showed the first discharge capacity of 115 mAh g⁻¹ at the current density of 0.064 mA cm⁻² and retained the reversible capacity of 110 mAh g⁻¹ after 10 cycles. The interfacial resistance was observed in the impedance spectrum of the all-solid-state cell charged to 4.4 V (vs. Li) and the transition metal elements were detected on the solid electrolyte in the vicinity of LiNi_1/3Co_1/3Mn_1/3O₂ by the TEM observations with EDX analyses. The electrochemical performance was improved by the coating of LiNi_1/3Co_1/3Mn_1/3O₂ particles with Li₄Ti₅O₁₂ film. The interfacial resistance was decreased and the discharge capacity was increased from 63 to 83 mAh g⁻¹ at 1.3 mA cm⁻² by the coating. The electrochemical performance of LiNi_1/3Co_1/3Mn_1/3O₂ was compared with that of LiCoO₂, LiMn₂O₄ and LiNiO₂ in the all-solid-state cells. The rate capability of LiNi_1/3Co_1/3Mn_1/3O₂ was lower than that of LiCoO₂. However, the reversible capacity of LiNi_1/3Co_1/3Mn_1/3O₂ at 0.064 mA cm⁻² was larger than that of LiCoO₂, LiMn₂O₄ and LiNiO₂.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

Lithium-ion battery anode properties of TiO2 nanotubes prepared by the hydrothermal synthesis of mixed (anatase and rutile) particles

From mixed (anatase and rutile) bulk particles, anatase TiO₂ nanotubes are synthesized in this study by an alkaline hydrothermal reaction and a consequent annealing at 300-400 °C. The physical and electrochemical properties of the TiO₂ nanotube are investigated for use as an anode active material for lithium-ion batteries. Upon the first discharge-charge sweep and simultaneous impedance measurements at local potentials, this study shows that interfacial resistance decreases significantly when passing lithium ions through a solid electrolyte interface layer at the lithium insertion/deinsertion plateaus of 1.75/2.0 V, corresponding to the redox potentials of anatase TiO₂ nanotubes. For an anatase TiO₂ nanotube containing minor TiO₂(B) phase obtained after annealing at 300 °C, the high-rate capability can be strongly enhanced by an isotropic dispersion of TiO₂ nanotubes to yield a discharge capacity higher than 150 mAh g⁻¹, even upon 100 cycles of 10 C-rate discharge-charge operations. This is suitable for use as a high-power anode material for lithium-ion batteries.     

Preparation and characterization of novel spinel Li4Ti5O12−xBrx anode materials

Br-doped Li₄Ti₅O₁₂ in the form of Li₄Ti₅O_12−xBr_x (0 ≤ x ≤ 0.3) compounds were successfully synthesized via solid state reaction. The structure and electrochemical properties of the spinel Li₄Ti₅O_12−xBr_x (0 ≤ x ≤ 0.3) materials were investigated. The Li₄Ti₅O_12−xBr_x (x = 0.2) presents the best discharge capacity among all the samples, and shows better reversibility and higher cyclic stability compared with pristine Li₄Ti₅O₁₂, especially at high current rates. When the discharge rate was 0.5 C, the Li₄Ti₅O_12−xBr_x (x = 0.2) sample presented the excellent discharge capacity of 172 mAh g⁻¹, which was very close to its theoretical capacity (175 mAh g⁻¹), while that of the pristine Li₄Ti₅O₁₂ was 123.2 mAh g⁻¹ only.