Synthesis of Co-coated lithium manganese oxide and its characterization as cathode for lithium ion battery

Co-coated LiMn₂O₄ was synthesized by electroless plating. The phase identification, surface morphology, and electrochemical properties of the synthesized powders were studied by X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, and galvanostatic charge–discharge experiments, respectively. The result shows that Co-coated LiMn₂O₄ particle has a coarse surface with a lot of holes. The specific capacity of Co-coated LiMn₂O₄ is 118 mAh g⁻¹, which is a bit less than 123 mAh g⁻¹ for the uncoated LiMn₂O₄. The capacity retention of Co-coated LiMn₂O₄ is 11% higher than the uncoated LiMn₂O₄ when the electrode is cycled at room temperature for 20 times. When cycled at the temperature of 55 °C, the capacity retention of Co-coated LiMn₂O₄ becomes 15% higher than the uncoated one.     

Synthesis and characterization of Cr8O21 as cathode material for rechargeable lithium batteries

Pure phase Cr₈O₂₁ with excellent electrochemical properties has been synthesized by sintering anhydrous chromium trioxide (CrO₃) at low temperature in flowing oxygen. Cyclic voltammetry (CV) and X-ray diffraction (XRD) characterizations indicate that the inner tetra-chromate groups of Cr₈O₂₁ are damaged and Cr₈O₂₁ is changed to another layer-structured material when lithium is inserted into the host.     

Inorganic polymer phosphazene disulfide as cathode material for rechargeable lithium batteries

Novel inorganic network polymer phosphazene disulfide [(NPS₂)₃]_n was synthesized by a solution cross-link method. IR and element content analysis confirmed the polymer's molecular structure. The polymer has an average particle size of d_0.5 = 7.7 μm and the specific surface area is 57.4 m² g^− 1. TG/DTA analysis showed that [(NPS₂)₃]_n underwent a decomposition reaction from 200 to 300 °C. When used as cathode material in lithium batteries, its initial discharge capacity was 459.1 mAh g^− 1, which is almost 93.5% of theoretical specific capacity (490.9 mAh g^− 1). After 30 charge–discharge cycles, the discharge capacity of [(NPS₂)₃]_n stabilized at approximately 400.1 mAh g^− 1 which revealed an excellent cyclic ability. Therefore [(NPS₂)₃]_n is of great potential as cathode material for secondary lithium batteries.     

Sulphide based anode material for lithium rechargeable battery

In this study, lead sulphide (PbS) was prepared by the chemical bath deposition technique. The sample was characterized by X-ray diffraction (XRD), Energy Dispersive Analysis of X-rays (EDAX) and cyclic voltammetry. EDAX spectrum shows peaks attributable to lead and sulphur. The EDAX analysis also shows that the prepared sample is stoichiometric. Cyclic voltammetry experiments were recorded at 100 mV·s⁻¹ and 400 mV·s⁻¹ scan rates. Results show that the rate controlling electrochemical reaction is electron transfer. The presence of redox waves shows that the lithium intercalation and deintercalation can occur as a result of lattice expansion in PbS. There were no differences in the PbS XRD data before and after the cyclic voltammetry experiments indicating that the PbS structure is not modified upon lithium ion intercalation and deintercalation in PbS. The discharge characteristics for 35 cycles of the cell using the LiCoO₂/PbS couple is presented indicating the possible development of such materials as anode in lithium ion cells.     

Pre-conditioned Li-rich layered cathode material for Li-ion battery

Solid solution material Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ (0.5Li₂MnO₃?0.5LiNi_0.4Co_0.2Mn_0.4O₂) is obtained through rheological phase method and further treated in ammonium persulfate solution. The post-treatment significantly decreases the charging capacity above 4.5 V and enhances the columbic efficiency in the initial cycle. Along with the higher efficiency, the cycling stability and the rate capability both get improved. The improvement mechanism is investigated in terms of XRD, XPS, Raman spectrometry, and ICP-AES. The results confirm that (NH₄)₂S₂O₈ treatment leads to Li⁺ removal from Li₂MnO₃ component while the layered structure of the solid solution phase is well maintained. After being treated in 30% (NH₄)₂S₂O₈ solution, 95% columbic efficiency is observed on Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ in the first cycle and it also shows a near 200 mAh g^?1 capacity at 4C current rate.     

Hydrothermal synthesis of spinel Li1+x Mn2O4 as cathode material for rechargeable lithium battery

Abstract

The hydrothermal synthesis of Li-Mn spinel oxide (Li_1+xMn₂O₄) was undertaken in order to develop high quality, low cost cathode material for a rechargeable lithium battery. In our experiments, γ-MnOOH, LiOH · H₂O and H₂O₂ were used as starting materials to synthesize Li-Mn spinel oxide under hydrothermal conditions of 180-230°C and about 1.0-2.8 MPa. The chemical composition and particle size of the Li_1+xMn₂O₄ is easily controlled in the hydrothermal reaction. The Li_1+xMn₂O₄ produced was characterized by X-ray diffraction, with the spinel phase having a Li/Mn ratio of 0.50-0.60. There is convincing evidence, as a result of this work, that our synthesis process is most suitable for producing high quality cathode material that can be used in a rechargeable lithium battery.     

First principles study on Mn-doped LiFePO4 as cathode material for rechargeable lithium batteries

The electronic structure and diffusion energy barriers of Li ions in pure and Mn-doped LiFePO4 have been studied using density functional theory （DFT）. The results demonstrate clearly that Fe - O covalent bond is weaker than P- O covalent bond. Pure LiFePO4 has band gap of 0.56 eV and diffusion energy barrier of 2.57 eV for Li ions, while the dopant has small band gap of 0.25 eV and low diffusion energy barrier of 2.31 eV, which indicates that the electronic and ionic conductivity of LiFePO4 have been improved owing to doping.     

Sn(II)-Treated MoO3 as cathode material for rechargeable lithium batteries

We report on the synthesis and structural, thermal and electrochemical characterisation of reduced molybdenum oxides with layered α-MoO₃ type structure. The samples have been prepared by reactions of various amounts of water-free tin dichloride with fine-particulated orthorhombic molybdenum trioxide in n-hexane (non-aqueous media) or in aqueous media, which yielded materials with different Sn:Mo ratio. XRD investigations of these materials proved that the crystal structure of the layered α-MoO₃ has been maintained after the reduction process. No crystalline impurity phases (e.g. tin oxides) could be detected by XRD. The tin-reduced samples exhibited a drastically improved cycling stability and capacity retention on cycling in 1 M LiClO₄/propylene carbonate, i.e. the discharge capacities were well above 100 mAh g⁻¹ after 20 cycles whereas the non-treated MoO₃ (reference sample) has retained only about 45 mAh g⁻¹. At higher cycle numbers (approx. cycle 100) the discharge capacity of the reduced molybdenum oxides stabilises at a level of approx. 100 mAh g⁻¹. This significant improvement of the rechargeability may be related to improved electronic conductivity and/or higher structural stabilisation of the layered MoO₃ structure either due to (i) a coating of the MoO₃ particles with a protective thin layer of a tin containing compounds, and/or (ii) an amorphisation of the structure after reductive treatment. Further efforts of this study were devoted to a variation of the conductive carbon content in the electrode composition and to changes of cut-off voltages and current densities. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Synthesis of PANI/rGO composite as a cathode material for rechargeable lithium-polymer cells

Graphene oxide (GO) was synthesized by an improved Hummers method and then reduced with NaBH₄; GO became rGO with regular layered structure. Polyaniline (PANI)/rGO composite was prepared by a adsorption double oxidant method with rGO as a template. Some physical characterization methods (Fourier transform infrared spectroscopy analysis, X-ray diffraction, scanning electron microscope, and transmission electron microscope) were used to analyze the morphology and crystallinity of the composite. The electrochemical properties were characterized by cyclic voltammetry, impedance spectroscopy, galvanostatic charge/discharge, and rate capability. The first discharge specific capacity of the rPANI/rGO and PANI/rGO was 181.2 and 147.8 mAh/g. After 100 cycles, the capacity retention rate was still 90.2 and 88.9% separately, and the coulombic efficiency of batteries is close to 100%. These results demonstrate the composite has exciting potentials for the cathode material of lithium-ion battery.     

First principles study on Mn-doped LiFePO4 as cathode material for rechargeable lithium batteries

The electronic structure and diffusion energy barriers of Li ions in pure and Mn-doped LiFePO4 have been studied using density functional theory(DFT).The results demonstrate clearly that Fe-O covalent bond is weaker than P-O covalent bond.Pure LiFePO4 has band gap of 0.56 eV and diffusion energy barrier of 2.57 eV for Li ions,while the dopant has small band gap of 0.25 eV and low diffusion energy barrier of 2.31 eV,which indicates that the electronic and ionic conductivity of LiFePO4 have been improved owing to doping.     

Synthesis and characterization of LiMnBO3 cathode material for lithium ion batteries

LiMnBO₃ with enhanced powder density was successfully synthesized by a commercially available spray-drying process. A monoclinic-LiMnBO₃ single phase was experimentally substantiated by an X-ray diffractometer with crystallinity investigated by Rietveld refinement method (Bragg R-factor and RF-factor <10). The dense LiMnBO₃ powder prepared by the spray drying process showed spherical morphology. The electrochemical property of LiMnBO₃ was extensively investigated, positively revealing that 0.27 Li⁺ (Li_0.27MnBO₃) was stoichiometrically extracted from the host LiMnBO₃ material at first cycle.     

Structural and electrical studies of LiMnVO4 cathode material for rechargeable lithium batteries

The lithium manganese vanadate (LiMnVO₄) cathode material was synthesized by using sol?Cgel method. The thermal behavior of the material has been examined by thermogravimetric and differential thermal analysis. The structure of LiMnVO₄ compound was studied by the Rietveld refined X-ray diffraction technique. Raman spectra showed that the local environment including VO₄ tetrahedra and LiO₆ octahedra as vibrational local units. X-ray photoelectron spectroscopy studies of synthesized LiMnVO₄ powder indicate that the oxidation states of manganese and vanadate are +2 and +5, respectively. The ionic conductivity of the sample is found to be 2.7?×?10^?5 Scm^?1 at 300?°C. The temperature dependent conductivity was conformed from the Arrhenius relation and the activation energy is found to be 0.3?eV. Dielectric spectra showed the decrease in dielectric constant with increase in frequency. Dielectric loss spectra reveal that dc conduction contribution predominates in the compound.     

Lithium-enriched polypyrrole as a prospective cathode material for Li-ion cells

Lithium substitution in polypyrrole can be accomplished by a variety of approaches and the present work introduces one of the cost-effective techniques using a relatively less expensive lithium salt, n-butyllithium in hexanes (n-BuLi), as the dopant. Chemical oxidative polymerization method is employed to synthesize polypyrrole (PPy) using anhydrous ferric chloride as the oxidant and it is dedoped using NH₄OH solution in the fully reduced state. The dedoped polypyrrole is treated with n-butyllithium in hexanes (n-BuLi) in an argon-filled glove box to get the lithiated form of polypyrrole (PPyL) and the concentration of n-BuLi is varied to improve metalation. The lithiated PPy is characterized by FTIR spectroscopy, XRD, FESEM, and TEM techniques to understand the structural and the morphological details. The lithium content in the lithiated samples is estimated using ICP-AES analysis. The thermal studies using the TGA technique show that the lithiated polypyrrole has good thermal stability. Coin cells are assembled in the argon-filled glove box using Li-substituted polypyrrole as the cathode, lithium metal foil as the anode, and lithium hexafluorophosphate (LiPF₆) as the electrolyte. The assembled cells are electrochemically characterized using cyclic voltammetry and charge–discharge cycling techniques and it is seen that the Li-substituted polypyrrole-based Li-ion cells are electrochemically active.     

Synthesis of LiCoPO4 as a cathode material for lithium-ion battery by a polymer method

A polymer method has been used to synthesize high operation voltage LiCoPO₄ cathode material. Thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM),galvanostatic charge–discharge test and cyclic voltammetry (CV) are used to study the LiCoPO ₄ . The results show LiCoPO₄ has a well-crystallized olivine structure with submicron size. In the range of 3.0–5.1 V, the initial discharge capacities of polymer material are 97.3, 91.5, and 86.5 mAh g^?1 at 0.1, 0.2. and 1 C, respectively. Thus, the polymer method has a great potential in preparing electrode materials for lithium-ion batteries.     

Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries

To improve the cycle performance of spinel LiMn₂O₄ as the cathode of 4-V-class lithium secondary batteries, spinel phases LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) were successfully prepared using the sol–gel method. The spinel materials were characterized by powder X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. Electrochemical studies were carried out using the Li|LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) cells. These cathodes were more tolerant to repeated lithium extraction and insertion than a standard LiMn₂O₄ spinel electrode in spite of a small reduction in the initial capacity. The improvement in cycling performance is attributed to the stabilization in the spinel structure by the doped metal cations.     

Layered lithium chromium manganese oxide compounds for high capacity electrode materials in rechargeable lithium batteries

A series of Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ cathode materials were prepared by the sol-gel process. The structural characterization was carried out by fitting the XRD data by the Rietveld method. The results of X-ray diffraction show that the crystal structure is similar to that of thelayered lithium transition metal oxides (R3-m space group). The particle morphology and size were observed by SEM, and the elemental content was determined by ICP. The electrochemical performance of the cathode was evaluated in the voltage range of 2.0 ∼ 4.9 V with a current density of 7.947 mA/g. The Li_1.27Cr_0.2Mn_0.53O₂ electrode delivered a high reversible capacity of around 280 mAh/g in cycling. Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ was found to be a promising cathode material. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Synthesis of PAN/SnCl2 composite as Li-ion battery anode material

A novel process was proposed to synthesize the pyrolytic polyacrylonitrile (PAN)/SnCl₂ composite anode material for Li-ion batteries. The preparation started with the dissolution of PAN and SnCl₂ in dimethylformamide (DMF), followed by drying of the solution and pyrolysis of the dried mixture of PAN and SnCl₂ at 300 °C, leading to homogenous dispersal of SnCl₂ in pyrolytic PAN, which becomes conducting polymer matrix. The composite presented stable cycling capacity of about 490 mAh/g. It is demonstrated that SnCl₂, which has been considered to be an inactive electrode material, can become active by the proposed composite technique. This paves the promising way to prepare electrode materials for Li-ion batteries.     

Structural stability in partially substituted lithium manganese spinel oxide cathode

LiMn₂O₄ is one of the most promising cathode materials for lithium secondary battery because of natural abundance of manganese in the crust and its low toxicity to environment. Lithium ion can almost reversibly intercalate into or deintercalate from lithium manganese spinel oxide LiMn₂O₄. A part of substitution of manganese with other transition metals brings the improvement of cycle life. We focused on the local structure of the spinels and considered the effect of the local distortion on the cycle life of the spinel cathodes. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Electrochemical performance of surfactant-processed LiFePO4 as a cathode material for lithium-ion rechargeable batteries

This study focuses on the effect of addition of surfactant as a dispersing agent during vibratory ball milling of LiFePO₄ (LFP) precursor materials on the electrochemical performance of solid-state reaction synthesized LFP for lithium-ion battery cathode material. LFP particles formed after calcinations of ball milled LFP precursors (Li₂CO₃, FeC₂O₄, and NH₄H₂PO₄) showed better size uniformity, morphology control, and reduced particle size when anionic surfactant (Avanel S-150) was used. The specific surface area of LFP particles increased by approximately twofold on addition of surfactant during milling. These particles showed significantly enhanced cyclic performance during charge/discharge due to a reduced polarization of electrode material. Electrodes fabricated from LFP particles by conventional milling process showed a 22 % decrease in capacity after 50 cycles, whereas the performance of electrode prepared by surfactant processed LFP showed only 3 % loss in capacity. The LFP particles were characterized using XRD, FE-SEM, particle size distribution, density measurement, and BET-specific surface area measurement. Electrochemical impedance spectra and galvanostatic charge/discharge test were performed for the electrochemical performance using coin-type cell.