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31.
Modified lithium manganese oxides were prepared by solid-state reaction of LiMn2O4 and LiCoO2 as raw materials. A study was carried out by TG-DSC,XRD, DSC and electrochemical to analyse the reaction process and structural characterization of products. The results show that the LiMn2O4 reacts chemically with LiCoO2 at high temperature. All of Li and partial Co atoms can insert into the LiMn2O4 crystal lattice and a newly formed spinel phase-modified LiMn2O4 was obtained. The distribution of Co content is even in modified LiMN2O4 compound. The modified LiMn2O4 compound exhibits improved cycling stability at room and elevated temperature in comparison with the pure LiMn2O4. 相似文献
32.
The insertion/removal processes of lithium ion in spinel lithium manganese oxide(LiMn204) and copper doped spinel lithium manganese oxide (LiCuxMn2-xO4) on a powder microelectrode were studied by electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV) and X-ray diffractometry(XRD). The insertion/removal process of lithium ion in the spinel oxides consists of three steps: charge transfer of lithium ion on the surface of the spinel oxides, diffusion and occupation of lithium ion in the lattice of the spinel oxide. Similar to chromium, the doping of copper in spinel lithium manganese oxide results in the increase of the charge transfer resistance and the double layer capacitance for lithium insertion or removal, and the decrease of the diffusion coefficient of lithium ion in the lattice of spinel oxide. However, the insertion capacitance, a parameter reflecting the occupation of lithium ion in the lattice of the spinel oxide, is hardly influenced by the doping of copper. The influence of the doped copper on the kinetic process of lithium insertion/removal in spinel lithium manganese oxide is related to the contraction of spinel lattice. 相似文献
33.
Zepan Wang Peiyuan Wu Xubing Zou Sheng Wang Lei Du Ting Ouyang Zhao-Qing Liu 《Advanced functional materials》2023,33(16):2214275
By using the more electro-negative Mn3+ ion to partially replace Co3+ at the octahedral site of spinel ZnCo2O4, i.e., forming ternary Zn–Mn–Co spinel oxide, the electrocatalytic oxygen reduction/evolution activity is found to be significantly increased. Considering the physical characterization and theoretical calculations, it demonstrated that the bond competition played a key role in regulating the cobalt valence state and the electrocatalytic activity. The partial replacement of octahedral-site-occupied Co3+ by Mn3+ can effectively modulate the adjacent Co–O bond and induce the Jahn–Teller effect, thus changing the originally stable crystal structure and optimizing the binding strength between the active center and reaction intermediates. Certainly, the Mn-substituted ZnMn1.4Co0.6O4/NCNTs exhibit higher electrocatalytic oxygen reduction reaction (ORR) activity than that of ZnCo2O4/NCNTs and ZnMn2O4/NCNTs, supporting that the Co–O bond covalency determines the ORR activity of spinel ZnCo2O4. This study offers the competition between adjacent Co–O and Mn–O bonds via the BOh–O–BOh edge-sharing geometry. The ion substitution at octahedral sites by less electronegative cations can be a new and effective way to improve the electrocatalytic performance of cobalt-based spinel oxides. 相似文献
34.
A combined hot-injection and heat-up method was developed to synthesize monodisperse and uniform CoMn2O4 quantum dots (CMO QDs).CMO QDs with average size of 2.0,3.9,and 5.4 nm were selectively obtained at 80,90,and 105 ℃,respectively.The CMO QDs supported on carbon nanotubes (CNTs) were employed as catalysts for the oxygen reduction/evolution reaction (ORR/OER) in alkaline solution to investigate their size-performance relationship.The results revealed that the amount of surface-adsorbed oxygen and the band gap energy,which affect the charge transfer in the oxygen electrocatalysis processes,strongly depend on the size of the CMO QDs.The CMO-3.9/CNT hybrid,consisting of CNT-supported CMO QDs of 3.9 nm size,possesses a moderate amount of surfaceadsorbed oxygen,a lower band gap energy,and a larger charge carrier concentration,and exhibits the highest electrocatalytic activity among the hybrid materials investigated.Moreover,the CMO-3.9/CNT hybrid displays ORR and OER performances similar to those of the benchmark Pt/C and RuO2 catalysts,respectively,due to the strong carbon-oxide interactions and the high dispersion of CoMn2O4 QDs on the carbon substrate;this reveals the huge potential of the CMO-3.9/CNT hybrid as a bifunctional OER/ORR electrocatalyst.The present results highlight the importance of controlling the size of metal oxide nanodots in the design of active oxygen electrocatalysts based on spinel-type,nonprecious metal oxides. 相似文献
35.
36.
通过葡萄糖辅助低温燃烧制备ZnO包覆型LiMn2O4,利用X射线衍射仪、扫描电子显微镜、循环伏安、交流阻抗以及恒流充放电测试等手段,研究了温度对产物晶体结构、微观形貌及电化学性能的影响。XRD结果表明所有产物均为单相尖晶石型LiMn2O4结构。SEM结果表明产物的颗粒尺寸随温度的升高而增大。电化学性能测试表明400℃和500℃制备的LiMn2O4/ZnO具有相对优异的电化学性能,室温1C条件下首次放电比容量分别为119.3mAh/g、116.3mAh/g,循环100次后容量保持率分别85.6%、87.8%。尖晶石LiMn2O4电极的阻抗谱特征与温度有关,电池的电化学性能主要受电荷转移电阻(Rct)影响。 相似文献
37.
基于离子交换机理,以ICSD(The Inorganic Crystal Structure Database)中LiMn_2O_4的结构数据为基础,利用Materials Studio软件包中Visualizer模块和CASTEP模块构建并优化了尖晶石型LiMn_2O_4和HMn_2O_4以及λ-MnO_2的晶体结构,并通过对比涉及各自晶体结构的系统能值、晶胞参数、键长及键角等的变化,初步验证了离子筛提锂过程是自发吸热过程;分别通过对LiMn2O4和HMn2O4添加H和Li,模拟考察了脱锂和嵌锂(即酸洗和吸附)过程中的活性原子位及H和Li的迁移轨迹,得出8a位置Li和H的离子性较强,脱锂为H置换四面体8a位置Li,并与邻近位置O形成键长约为0.098 9nm的O-H键;嵌锂为Li取代8a-16c-8a孔道中8a位置H的动力学过程。研究结果对锰基离子筛提锂的后续工作具有一定的指导意义。 相似文献
38.
通过2205双相不锈钢渣-钢反应平衡实验,得到不同炉渣配比下的MgO-Al_2O_3二元系固溶体夹杂,当反应达到平衡后,向钢中添加了0.05%的Ti,进而得到了"MgO-Al_2O_3固溶体+TiN"的复合夹杂。试样经水淬后,通过电镜分析夹杂物,然后采用10%的草酸进行电解,与不加Ti的铸态组织δ铁素体晶粒形貌、尺寸进行了对比。实验结果发现:TiN析出量随MgO-Al_2O_3固溶体中Al_2O_3比例的增加而增加,铸态δ铁素体晶粒可得到明显细化,实验结果发现富MgO的MgO-Al_2O_3固溶体以及MgO·Al_2O_3析出TiN很少,δ铁素体细化效果不明显。通过热力学计算、异质形核理论以及实验结果证明,MgO-Al_2O_3二元系固溶体夹杂物成分由炉渣成分及钢中Mg、Al活度共同决定,MgO-Al_2O_3固溶体中Al_2O_3含量增加,使MgO·Al_2O_3晶格发生畸变,这与点阵中存在着空位密切相关。由于空位富集,使得点阵常数e不均匀,也由于空位改变晶格场,引起O2-的移动或转移,形成缺位尖晶石固溶体。晶格的能量状态发生变化促进了Ti原子和N原子在MgO-Al_2O_3夹杂物表面析出。 相似文献
39.
Chris E. Mohn 《Materials and Manufacturing Processes》2018,33(2):174-179
Genetic algorithms (GAs) together with classical pair potentials and density functional theory (DFT) are used to investigate cation order in MgAl2O4 (Spinel). To efficiently locate the global minimum/minima on the system potential energy surface, corresponding to the ordered and fully equilibrated low-temperature phase, local structural optimizations are essential. Such energy minimizations are expensive at the DFT level, but a comparison of the distribution of the energy minima from DFT and popular classical pair potentials allows one to rapidly tune the GA parameters. We show that GAs are able to find, not only the global minimum on the potential energy, but also other low-energy cation configurations representing possible frozen-in disordered or metastable phases after quenching. The nature of these low-energy configurations can help to interpret the extent of kinetic trapping which hampers the comparison between different experimental studies. 相似文献
40.
以苯酚过氧化氢羟基化制取苯二酚为背景,采用共沉淀法制备了对苯酚过氧化氢羟基化具有高活性的含硅的铁酸镁(MgxFey(SiO4))尖晶石类催化剂,对所制备的含硅的该催化剂的结构进行了分析表征,并研究了它们的苯酚羟化活性。 相似文献