Hydrothermal synthesis of LiMnO2 microcubes for lithium ion battery application

Two kinds of LiMnO₂ microcubes were successfully synthesized by hydrothermal method using solid or hollow Mn₂O₃ microcubes as precursors. One was made up of nanoparticles varying in size and the other was made up of interlaced polygonal nanoplates with the thickness of 70 nm. Both kinds of LiMnO₂ microcubes were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Charge–discharge curves were carried out to investigate their electrochemical properties. LiMnO₂ microcubes with interlaced nanoplates showed much better capacities than the ones with nanoparticles indicating it is more suitable for application in the lithium ion batteries. The former material could deliver the capacities of 197 and 134 mAh/g at 0.1 and 1 C, respectively. And its capacity fading after 50 cycles did not exceed 7 %. The excellent electrochemical performance of the former material could be ascribed to the smaller size which could shorten the path length for lithium ion transport and increase the electrode and electrolyte contact.     

Magnetic properties of lithium intercalation compounds

Magnetic experiments are powerful tools to study fundamental properties and to check the qualities of samples. Temperature, stress, and impurities of materials can all affect magnetic properties and play an important role in the utilization of these materials for engineering applications. The estimation and analysis of the spontaneous magnetization can reveal ferromagnetic particles as impurities in samples. The shape of the temperature dependence of magnetization is indicative of the origin of the magnetic properties. However, it is necessary to correlate the χ _m (T) curves and isothermal M(H) plots to achieve a complete analysis of the electronic properties of the materials. Highlights of magnetic properties of lithium intercalation compounds are briefly described. Intrinsic and extrinsic properties are considered as useful parameters to determine the purity of electrode materials for rechargeable Li-ion batteries.     

High precision studies of lattice parameter changes in lithium intercalation compounds

We present an in situ X-ray diffraction experiment which measures lattice parameter changes resulting from lithium intercalation to a precision of one part in 10⁵. Experiments on 2H-Li_xTaS₂ demonstrate the sensitivity and reproducibility of the method. To our knowledge, these results are the most precise measurments of lattice parameter changes resulting from intercalation. We find that the c-axis of 2H-Li_xTaS₂ exhibits anomalous behaviour near $\text{x=}\text{1}\text{3}$ and $\text{x=}\text{2}\text{3}$ pr esumably because of the order-disorder transitions in the intercalated lithium.     

Effect of a rhombohedral phase on lithium intercalation capacity in graphite

Five natural graphites with different rhombohedral phase (3R phase) content have been investigated as anode materials for rechargeable lithium-ion batteries. The reversible capacity varies from 250 mA h/g to 350 mA h/g for the same intercalation conditions depending on the content of the 3R-phase. With increasing rhombohedral phase in the graphite, the intercalation capacity will be high. A peak at about 10 mV in the cyclic voltammograms (CV) of a sample with a large 3R-phase content is caused by lithium ions occupying boundaries between the rhombohedral (3R) phase and the hexagonal (2H) phase and is responsible for a capacity exceeding the theoretical value.     

High pressure properties of graphite and its intercalation compounds

The effects of applied pressure on graphite and its intercalation compounds are reviewed emphasizing the relationship between structure and transport properties. It has long been recognized that high pressure plays a crucial role in the polymorphic phase transitions of graphite, notably in the graphite-diamond transformation. More recent studies have revealed a wealth of pressure-induced phases associated with the unusual layer-stacking (‘staging’) mechanism in the intercalation compounds of graphite. The high degree of structural anisotropy associated with staging is strongly reflected in the electronic band structure and transport properties, and in the remarkable pressure dependence of the superconducting states of some of the graphite intercalation compounds. High pressure is shown to be a valuable means not only to realize new structural phases but also to improve our understanding of the fundamental behaviour of these important materials.     

Chemistry, structure and electrochemistry of new lithium intercalation compounds synthesized via low temperature techniques

The present work exemplifies the interest of using the soft chemistry route to obtain high performance cathodic materials for rechargeable lithium batteries. Significant progress may be made either in obtaining new compounds or in providing improvements to the electrochemical performance of oxides already known. Two synthesis ways are developed in our laboratory: the sol-gel process and precipitation reactions. The electrochemical behaviour of three main groups of Li intercalation compounds is investigated and discussed in relation with the specific chemical and structural properties induced by the synthesis way. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Hydrothermal synthesis of FeS2 for lithium batteries

Nanocrystalline FeS₂ cathode material of lithium cell was synthesized from cheap materials of FeSO₄, Na₂S₂O₃, and sulfur by a hydrothermal process. The scanning electron microscopy analysis showed the obtained material was nano-sized, about 500 nm. The X-ray powder diffraction analysis showed that the synthetic FeS₂ material had two phases of the crystalline structure, pyrite and marcasite. The phase of marcasite seems to have no negative effect on the electrochemical performance of the material. The synthetic FeS₂ showed a significant improvement of electrochemical performance for Li/FeS₂ cells.     

Studies of lithium intercalation in 3R-WS2

The lithium intercalation into the layered dichalcogenide 3R-WS₂ has been investigated by electrochemical reduction and by chemical reaction in n-butyl lithium solution. Essential results are (a) a charge transfer of nearly 0.6e⁻/W in Li_xWS₂, (b) a small increase of the c-axis parameter of about 0.6%, and (c) a high mobility of the Li⁺-ions. The chemical diffusion coefficient of Li⁺-ions is estimated to be 8 × 10⁻⁹ cm² s⁻¹ in the composition range 0 ≤ x ≤ 0.25. The appearance of a structural transformation from 3R-WS₂ to 2H-Li_xWS₂ is interpreted on grounds of instabilities in the interlayer structure.     

A galvanostatic study of lithium intercalation in RuO2

The diffusion process in a host structure has been studied at constant current with the cells: RuO₂ composite/ LiClO₄PEO/Li and RuO₂ powder/LiClO₄PC/Li. The effect of grain size distribution and temperature has been investigated and the diffusion coefficient for Li in RuO₂ calculated along with the diffusion activation energy (0.52 eV). Results show no intercalation of PC at 25°C.     

锂离子电池SnSb/MCMB核壳结构负极材料嵌锂性能研究

以酸处理的中间相碳微球(MCMB)为载体, 用化学还原法在碳球表面沉积SnSb合金, 合成SnSb 包覆碳球的核壳结构负极材料. 采用XRD, SEM技术对材料的结构和形貌进行了表征, 用恒电流充放电(CC)、循环伏安(CV)和交流阻抗(EIS)测试了材料的电化学性能. 实验结果表明: SnSb/MCMB样品呈现纳米晶与非晶态的混合组织; 单一SnSb合金的容量衰减较快, 而对于SnSb/MCMB复合材料, 细小的合金颗粒均匀钉扎在MCMB表面, 不仅改善了颗粒的团聚现象, 而且增强了材料的导电能力, 使材料的循环稳定性得到改善, 复合材料具有936.161 mAh/g的首次放电比容量, 首次库仑效率80.3%, 50次循环后容量维持在498.221 mAh/g. 关键词： SnSb合金 锂离子电池 中间相碳微球(MCMB) 电化学性能     

Dip-coated silver-doped V2O5 xerogels as host materials for lithium intercalation

Vanadium pentoxide xerogels have shown high electrochemical performance in terms of energy content. The high specific energy and high intercalation capability make the materials promising for thin film lithium battery and electrochromic device applications. In order to enhance the rate capabilities of the host we increased the electronic conductivity by doping the V₂O₅ xerogels with silver. Samples were prepared by mixing various amounts of silver powder with V₂O₅ hydrogel. We were able to prepare silver-doped vanadium pentoxide dip-coated thin films with a molar ratio (Ag/V) ranging from 0.005 to 0.5 (Ag_yV₂O₃ with y = 0.01, 0.1 and 1). With the successful doping, the electronic conductivity of V₂O₅ was increased by 2 to 3 orders of magnitude. The insertion capacity of the material was maintained and up to 4 moles of lithium per mole of silver-doped V₂O₅ (XRG) were found to be reversibly intercalated.     

Magnetic susceptibility and band structure of intercalation compounds of 2H-TaS2

A universal correlation is reported between the magnetic susceptibility of the TaS₂ layers at 300 K and the population (1 to 2 e^-/TaS₂) of the TaS₂ conduction d-band in intercalation compounds of 2H-TaS₂. From this curve, the variation in the density of states at the Fermi level D(E_F) with E_F was derived; good agreement with the variation predicted by band structure calculations for 2H-TaS₂ was found.