锂离子电池正极材料LixMn2O4研究进展

总结了锂离子电池正极材料LixMn2O4的合成方法，归纳了造成容量衰减问题的原因和目前为解决该问题所采用的各种方法，并且对下一步的研究工作进行了展望。     

采用不同锰源合成尖晶石LiMn2O4正极材料

The spinel LiMn2O4 cathode material was synthesized with the solid-state reaction method. Four manganese compounds including electrolytic manganese dioxide (EMD), MnCO3, Mn3O4 and nano-EMD were used as Mn sources while LiOH·H2O was used as the uniform Li source. The crystal structure characteristics of these samples produced were investigated by means of XRD, SEM, particle size distribution analysis and specific surface area testing. Their electrochemical properties were also studied by comparing their specific capacity, charge and discharge efficiency and cycle performance.     

Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene

New tetradentate chelates of bis-Schiff bases were synthesized and then these chiral salen ligands were immobilized over mesoporous MCM-41 by using the ion-exchange method. The efficiency of the chiral catalyst was examined in the asymmetric epoxidation of styrene. Chiral Mn(salen) complexes immobilized onto mesoporous MCM-41 were stable during the reaction without any leaching and exhibited relatively high enantioselectivity for epoxidation as compared with homogeneous complexes. This revised version was published online in August 2006 with corrections to the Cover Date.     

DUO-ICP-AES测定精对苯二甲酸中的钴、铬、铁、锰、钼、镍、钛

采用DUO-ICP-AES同时测定精对苯二甲酸中钴、铬、铁、锰、钼、镍、钛,并对仪器的分析线选择、背景校正、入射功率、雾化器压力、辅助气流量、冷却气流量、蠕动泵转速的影响及共存元素的干扰、硝酸铯灰化助剂等因素进行了详细的研究。方法的检测限:钴0.0097 mg/L;铬0.0021 mg/L;铁0.0078 mg/L;锰0.0012 mg/L;钼0.0027 mg/L;镍0.016 mg/L;钛0.0027 mg/L,回收率和精密度分别为93.0%～99.5%和0.37%～3.2%。该方法快速简便,具有良好的精密度和准确度,适用于进出口精对苯二甲酸的日常检验。     

Variable temperature13C MAS NMR of KFe2Mn(CO)12 in the solid state and as aCatalyst precursor on a carbon support

Variable temperature¹³C MAS NMR spectra are reported for¹³CO-enriched KFe₂Mn(CO)₁₂ as a solid and also as dispersed clusters on a carbon support. The spectrum of KFe₂Mn(CO)₁₂ at 300 K agrees with the proposed structure for this cluster and shows that the cluster is static. Two bridging carbonyl resonances are clearly resolved and, by comparison with¹³C MAS NMR spectra of Mn₂(CO)₁₀ and Fe₂(CO)₉, all terminal resonances for the cluster can be assigned. When the cluster is supported on carbon, two broad resonances are observed at room temperature which are assignable to KFe₂Mn(CO)₁₂ and a decomposition product, Mn₂(CO)₁₀. The carbonyl ligands in both supported clusters are completely averaged, and KFe₂Mn(CO)₁₂ on the carbon surface demonstrates fluxional behavior similar to that observed for the cluster in solution. For this fluxional process, activation energies of 0.6 kcal/mol and 0.5 kcal/mol are estimated for carbon-supported KFe₂Mn(CO)₁₂ and Mn₂(CO)₁₀, respectively.     

溶胶凝胶法制备LiNi0.01Co0.01Mn1.98O3.95F0.05及其电化学性能

采用溶胶凝胶法合成锂离子电池正极材料LiMn2O4、LiNi0.01Co0.01Mn1.98O4和LiNi0.01Co0.01Mn1.98O3.95F0.05。使用X射线衍射、扫描电子显微镜对合成材料的结构及物理性能进行了表征。将合成材料作为锂离子电池正极活性材料,用循环伏安、交流阻抗及充放电测试的电化学测试方法对材料进行了电化学的研究。结果表明,合成的LiNi0.01Co0.01Mn1.98O3.95F0.05材料的初始容量高于LiNi0.01Co0.01Mn1.98O4,而循环性能优于LiNi0.01Co0.01Mn1.98O4和LiMn2O4,显示了阴阳离子复合掺杂对于阳离子单一掺杂的优势。     

Evaluation of chromium release during the decomposition of leather meal fertilizers applied to the soil

Greenhouse studies of 14 soils, having a range in DTPA extractable Mn, were made to determine the critical deficiency level of Mn in ustochrepts for predicting response of green gram to Mn application. Soil Mn was significantly related with Bray's per cent dry matter yield (r = 0.68^**). Soil application of 20 mg Mn kg^–1 soil significantly increased the yield. Both graphical and statistical models of Cate and Nelson indicated the critical level to be 2.9 mg kg^–1 soil of DTPA extractable Mn. The critical deficiency level in youngest matured terminal leaf (YML) of 40 day green gram plants was 19.0µg g^–1. The predictability of soil and plant critical Mn level was 93 per cent.     

铸钢件黑色磷化工艺的研究

通过对黑色磷化各种工艺因素的研究,确定了铸钢件锰系中温黑色耐磨磷化工艺的最佳方案.采用体视显微镜研究了磷化膜表面微观形貌;采用X射线荧光光谱法(XRF)对磷化膜的厚度和成分进行了测定;采用点蚀法对磷化膜的耐蚀性进行了研究.结果表明,磷化膜性能好,磷化液污染小,便于维护和调整;温度适中,节约能源.本文还对磷化液中各成分作用进行了理论分析.     

Effect of structural and electrochemical properties of different Cr-doped contents of Li[Ni1/3Mn1/3Co1/3]O2

Layered Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Cr_x]O₂ materials with x = 0, 0.01, 0.02, 0.03, 0.05 are prepared by a solid-state pyrolysis method. The oxide compounds were calcined with various Cr-doped contents, which result 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−x)/3Mn_(1−x)/3Co_(1−x)/3Cr_x]O₂ powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and SEM. XRD experiment revealed that the Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Cr_x]O₂ (x = 0, 0.01, 0.02, 0.03, 0.05) were crystallized to well layered -NaFeO₂ structure. The first specific discharge capacity and coulombic efficiency of the electrode of Cr-doped materials were higher than that of pristine material. When x = 0.02, the sample showed the highest first discharge capacity of 241.9 mAh g⁻¹ at a current density of 30 mA g⁻¹ in the voltage range 2.3–4.6 V, and the Cr-doped samples exhibited higher discharge capacity and better cycleability under medium and high current densities at room temperature.     

Coexistence of antiferromagnetic and ferromagnetic in Mn-doped anatase TiO2 nanowires

A series of Mn-doped TiO_2 nanowires (NWs) were prepared by hydrothermal method at the mole fraction of Mn changing from 0 to 12.0%. X-ray powder diffraction (XRD) analysis shows that all the samples have pure anatase structure. SEM and TEM studies show that the diameter and the length of the Mn-doped TiO_2 NWs are larger than those of the undoped TiO_2 NWs. Energy dispersive X-ray spectroscopy (EDX) reveals that the samples are composed of Ti, Mn and O. According to magnetization measurements, all samples show ferromagnetic behavior, but only the undopedTiO_2 NWs are completely ferromagnetic with a saturated magnetization about 1.0 mA·m~2/kg. Mn-doped TiO_2 samples exhibit antiferromagnetic and ferromagnetic (AF-FM) behaviors simultaneously. Photoluminescence (PL) spectra demonstrate the existence of MnO_2 sublattice. These observations indicate that an AF-WF crossover is induced by the coexistence of TiO_2 sublattice and MnO_2 sublattice.