Synthesis and electrochemical properties of HT-LiCo0.8Ni0.2O2 prepared by molten salt synthesis method using 0.59LiNO3-0.41LiOH system

LiCo_0.8Ni_0.2O₂ powders were prepared by molten salt synthesis method using a 0.59LiNO₃-0.41LiOH melt. The physico-chemical properties of the HT-LiCo_0.8Ni_0.2O₂ powders were investigated by powder X-ray diffraction method, field emission scanning electron microscopy, cyclic voltammetry, and charge-discharge cycling. Uniform size nanocrystalline powder (~40 nm) could be obtained at temperature ranges of 280-480 °C. These nanocrystalline powders showed poor electrochemical properties because of presence of the low temperature phase. Pure single-phase HT-LiCo_0.8Ni_0.2O₂ powder could be obtained at 580 °C. Charge-discharge measurements indicated that this exhibited a good capacity and cyclability without further heat treatment at higher temperatures. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

High-strength Ti2AlN ceramics prepared by pulse electric current sintering based on powders synthesized by molten salt method

Ti₂AlN powders were synthesized through molten salt method and re-calcination process using TiH₂, Al and TiN powders as raw materials at 1100 ℃. The composition of final composite was directly influenced by the initial Al and TiH₂ content in the starting mixture. The purity of the synthesized Ti₂AlN powder could reach 97.1 wt% when the Al molar ratio was 1.05. Then high strength Ti₂AlN ceramics were successfully prepared in different modes, including two forms of pulse electric current sintering (PECS/SPS) and hot-pressing sintering (HP). A record-high flexural strength of 719 MPa was obtained for the PECS/SPS with an electrical insulating die (PECS/SPS II) sintered sample, based on the synthesized powder in which the initial molar ratio of Al was 1.1. The sintering behaviors in various modes were analyzed, confirming the shrinkage of particles starting at lower temperature in PECS/SPS II. The density, microstructure, Vickers hardness and elastic modulus of sintered ceramics were also investigated. Therefore, the present work provided the new methods about powder preparation and ceramic sintering of Ti₂AlN, making it possible to be used as high strength structural ceramics.     

Structure,electrical properties and reaction mechanism of (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 ceramics synthesized by the molten salt method

Lead-free (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ (BCZT) ceramics with excellent electrical properties were successfully synthesized by a molten salt method (MSS). The submicron BCZT powders with pure perovskite phase were obtained by adjusting the KCl-NaCl content that was used as the eutectic salt. The effects of salt content and reaction temperature on the structure and properties of the BCZT materials were systematically investigated. Comparing with BCZT ceramics prepared by solid state method (SS), the reaction temperature of BCZT ceramics synthesized by MSS decreased approximately 200 °C. Moreover, BCZT ceramics sintered at 1360 °C with 50% eutectic salt showed the most outstanding electrical properties, which are as follows: d₃₃ = 604 pC/N, k_p = 57%, P_s = 17.11 µC/cm², P_r = 9.98 µC/cm², ε_m = 15872, ε_r = 2654 and tan δ = 0.013. In addition, this work revealed a possible reaction course processes and mechanism about MSS. The results provide a new design to optimize the performance of BCZT lead-free piezoelectric ceramics.     

Surface modification of LiMn2O4 cathode with LaCoO3 by a molten salt method for lithium ion batteries

Spinel LiMn₂O₄ is a promising cathode due to its advantages of low-cost, nontoxicity and thermal stability. However, the dissolution of manganese and the phase transformation induce the rapid capacity fade. Surface coating is an effective method to improve its electrochemical performance. In this work, spinel LiMn₂O₄ modified with perovskite LaCoO₃ was prepared using a novel molten salt method. The resulted samples were characterized by X-ray diffraction (XRD), transmission/scanning electron microscopy (TEM/SEM), Fourier transformation infrared (FT-IR), Raman, and X-ray photoelectronic spectroscopy. The content of Mn³⁺ increased with the LaCoO₃ coating accompanied by the increased concentration of oxygen vacancy. LiMn₂O₄ modified with 2% LaCoO₃ shows a higher capacity and cycling stability than others at 0.2 C, while the cathode with 4% LaCoO₃ shows the best rate performance at a larger current at 2 and 5 C. This enhanced performance can be attributed to improved interfacial conductivity between the cathode and electrolyte and the protective effects of coating.     

Structural and electrochemical characteristics of Li0.7[Li1/6Mn5/6]O2 synthesized using sol-gel method

Layered O₂-lithium manganese oxide (O₂-Li_0.7[Li_1/6Mn_5/6]O₂) was prepared by ion-exchange of P2-sodium manganese oxide (P2-Na_0.7[Li_1/6Mn_5/6]O₂)· P2-Na_0.7[Li_1/6Mn_5/6]O₂ precursor was first synthesized by using a sol-gel method, and then O₂-Li_0.7[Li_1/6Mn_5/6]O₂ was produced by an ion exchange of Li for Na in the P2-Na_0.7[Li_1/6Mn_5/6]O₂ precursor. Structural and electrochemical analyses suggested that good quality O2-Li_0.7[Li_1/6Mn_5/6]O₂ was prepared from P2-Na_0.7[Li_1/6Mn_5/6]O₂ synthesized at 800 °C for 10 h using glycolic acid as a chelating agent. During the cycle, the discharge profile of the synthesized samples showed two plateaus at around 4 and 3 V, respectively, with a steep slope between the two plateaus. The discharge curve at 3 V escalated with an increase in the cycle number, presenting a phase transition from a layered to a spinel like structure. The sample prepared at 800 ‡C for 10 h using glycolic acid delivered a discharge capacity of 187 mAh/g with small capacity fading.     

氨分解制氢棒状LaxCe1-xOy负载Ru催化剂

氨分解得到的H₂不含CO _x 、SO _x 、NO _x 等有害物质,是其他所有含碳资源为原料制氢所不能比拟的。本文采用无模板水热法制备了一系列棒状载体,并采用沉积沉淀法制备了Ru/La _x Ce_1-x O _y 催化剂,考察了制备方法、催化剂组成对性能的影响,并通过扫描电镜（SEM）、X射线衍射（XRD）、BET、H₂-程序升温还原（TPR）和CO₂-程序升温脱附（TPD）进行了表征。结果表明,La₂O₃掺杂量为40%的Ru/La_0.4Ce_0.6O_1.8催化剂在常压、7800h^-1、450℃下氨分解转化率为98%。该催化剂活性高归因于部分还原的CeO_2-x 对Ru的供电子性能和Ru/La_0.4Ce_0.6O_1.8催化剂表面的强碱性增加了对Ru活性位的给电子能力。同时考察了K₂O含量的影响,最优的催化剂为Ru-2%K/La_0.4Ce_0.6O_1.8,在400℃、7800h^-1氨气转化率可以达到93%。结果表明Ru-2%K/La_0.4Ce_0.6O_1.8可以作为一种新型高效氨分解催化剂,为工业化应用提供了可能,具有良好的发展前景。     

共沉淀法制备Li[Ni1/3Co1/3Mn1/3]O2及电化学性能研究

采用NH3-NaOH共沉淀法合成了L[Ni1/3Co1/3Mn1/3]O2正极材料,通过改变NH3·H2O浓度及加料方式研究材料的电化学性能.采用XRD、SEM对晶体的结构和形貌作表征.将正极材料Li[Ni1/3Co1/3Mn1/3]O2制成电极极片,组装成电池进行测试.分析测试结果表明,合成的极材料Li[Ni1/3Co1/3Mn1/3]O2具有典型的α-NaFeO2结构,粒径分布较好,呈类球形.     

不同沉淀剂对Li_(1.1)Ni_(0.5)Mn_(0.5)O_2结构和电化学性能的影响

通过共沉淀-高温煅烧方法合成了层状结构的Li1.1Ni0.5Mn0.5O2正极材料,并通过XRD、SEM研究了不同沉淀剂对产物结构和形貌的影响。运用恒电流充放电测试、CV及EIS研究了其电化学性能。结果表明,不同沉淀剂合成的产物均具有良好的层状结构及形貌。碳酸盐为沉淀剂合成的产物锂镍混排度最小,颗粒更均匀,具有最低的极化及最小的电荷转移阻抗,具有最高的容量及最优的倍率性能。     

Improved electrochemical performance of Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries synthesized by the polyvinyl alcohol assisted sol-gel method

Li-rich Mn-based cathode materials (Li_1.2Ni_0.2Mn_0.6O₂) have been synthesized by a polyvinyl alcohol (PVA)-assisted sol-gel method. The influence of PVA content on the structure and electrochemical performance of Li_1.2Ni_0.2Mn_0.6O₂ has been investigated respectively. XRD results of the Li_1.2Ni_0.2Mn_0.6O₂ powders show that they exhibit similar XRD patterns as those of Li-rich Mn-based cathode materials, and the crystalline nature of the layered compound are improved by the presence of PVA. Physical characterizations indicate that the as-synthesized oxide is composed of uniform and separated particles compared to the larged aggregated ones of the product synthesized under the same condition but without PVA. As cathode for lithium ion battery, the material synthesized with 10% PVA exhibits not only a relatively high discharge capacity of 254.2 mA h g⁻¹, but also excellent rate performance and good cycling performance. EIS results show that the material synthesized with PVA decreases the charge-transfer resistance and enhances the reaction kinetics, which is considered to be the major factor for higher rate performance.     

Influence of Zn-substitution on structural,morphological, electrical,and gas sensing properties of ZnxAl2O4 (x = 0.1 to 0.5) synthesized by a sol-gel auto-combustion method

The nanosphere decorated needle-like morphology of zinc-substituted aluminate having general formula Zn_xAl₂O₄ (x = 0.1, 0.2, 0.3, 0.4, and 0.5) (ZAN) samples were synthesized by a sol-gel auto-combustion method. The phase formation and stability temperature were confirmed by TG-DTA analysis. XRD study confirmed the formation of a cubic spinel structure of ZAN samples. The effect of Zn-substitution on structural and morphological properties of aluminate were investigated using X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM), and Energy dispersive X-ray analysis (EDAX). The D.C. electrical resistivity study of ZAN samples revealed that resistance decreased with increasing temperature confirmed semiconducting nature. Nanosphere existing on micro-needles of zinc-substituted aluminate gas sensor revealed sensing to several analyte gases such as H₂S, Cl₂, CH₃OH, SO₂, and NO₂ working at room temperature to 300 ^°C. The Zn_0·4Al₂O₄ compositional gas sensor produced the highest response at operating temperature 200 ^°C to 100 ppm H₂S. The results revealed that the prepared nanosphere decorated needles of the ZAN sensor was sensitive and selective to H₂S gas.