Quantum mechanical modeling of Zn-based spinel oxides: Assessing the structural,vibrational, and electronic properties

The structural, electronic, and vibrational properties of two leading representatives of the Zn-based spinel oxides class, normal ZnX₂O₄ (X = Al, Ga, In) and inverse Zn₂MO₄ (M = Si, Ge, Sn) crystals, were investigated. In particular, density functional theory (DFT) was combined with different exchange-correlation functionals: B3LYP, HSE06, PBE0, and PBESol. Our calculations showed good agreement with the available experimental data, showing a mean percentage error close to 3% for structural parameters. For the electronic structure, the obtained HSE06 band-gap values overcome previous theoretical results, exhibiting a mean percentage error smaller than 10.0%. In particular, the vibrational properties identify the significant differences between normal and inverse spinel configurations, offering compelling evidence of a structure-property relationship for the investigated materials. Therefore, the combined results confirm that the range-separated HSE06 hybrid functional performs the best in spinel oxides. Despite some points that cannot be directly compared to experimental results, we expect that future experimental work can confirm our predictions, thus opening a new avenue for understanding the structural, electronic, and vibrational properties in spinel oxides.     

Preparation and performance of (Co,Mn)3O4 spinel coating on Crofer alloy by composite electrodeposition and step-heating thermal conversion

The preparation and performance improvement of the spinel coating on the surface of ferritic alloy is of wide interest for its application in the metallic interconnects of the solid oxide fuel cells (SOFCs). The Co Mn₂O₃ composite coating is prepared on the surface of the Crofer alloy by the composite electrodeposition method. A step-heating thermal conversion process is subsequently used to convert the composite coating into a spinel coating, while a direct-heating process is implemented as the control experiment. Isothermal oxidation tests are then carried out for the prepared samples in order to present the high temperature performance. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and area-specific resistance (ASR) are used to analyze the properties of the matrix and coatings. The experimental results reveal that the coatings by step-heating thermal conversion exhibit better performance of electrical conductivity and oxidation resistance than the coatings by direct-heating process. Furthermore, with the increase of oxidation time, the atomic proportion of Cr element diffusing to the surface of the matrix is maintained at about 3%–4% for the samples with spinel coatings by step heating, which effectively prevent the Cr volatilization in the matrix. The preparation of spinel coatings on the ferritic alloy by composite electrodeposition and step-heating thermal conversion is helpful to stimulate new ideas for the development of reliable and cost-effective metallic interconnect.     

Frenkel‐Defect‐Mediated Chemical Ordering Transition in a Li–Mn–Ni Spinel Oxide

Using spinel‐type Li(Mn_1.5Ni_0.5)O₄ with two different cations, Mn and Ni, in the oxygen octahedra as a model system, we show that a cation ordering transition takes place through the formation of Frenkel‐type point defects. A series of experimental results based on atomic‐scale observations and in situ powder diffractions along with ab initio calculations consistently support such defect‐mediated transition behavior. In addition to providing a precise suggestion of the intermediate transient states and the resulting kinetic pathway during the transition between two phases, our findings emphasize the significant role of point defects in ordering transformation of complex oxides.     

溶胶-凝胶法制备NixCo1-xCoAlO4尖晶石型复合氧化物及其催化分解N2O性能

用溶胶凝胶法制备了一组Ni_xCo_1-xCoAlO₄尖晶石型复合氧化物,并采用表面润湿浸渍K₂CO₃溶液进行了K掺杂改性,用于有氧气氛下的N₂O催化分解反应.采用N₂物理吸附、X-射线衍射(XRD)、扫描电镜(SEM)、H₂-程序升温还原(H₂-TPR)等技术对催化剂进行了表征,考察了催化剂组成、母液pH值、K负载量等制备参数对其催化活性的影响.结果表明,母液pH值为3、K/(Ni+Co)物质的量比为0.1的K/Ni_0.15Co_0.85CoAlO₄催化剂具有较高的N₂O分解活性,450 ℃ N₂O可完全分解.助剂K的加入弱化了催化剂表面金属氧键,提高了催化剂的还原性、催化活性和抗水性.     

Fast Li-Ion Conduction in Spinel-Structured Solids

Spinel-structured solids were studied to understand if fast Li⁺ ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically active solid solution of the Li⁺ stuffed spinel with spinel-structured Li-ion battery electrodes. This could enable a single-phase fully solid electrode eliminating multi-phase interface incompatibility and impedance commonly observed in multi-phase solid electrolyte–cathode composites. Materials of composition Li_1.25M(III)_0.25TiO₄, M(III) = Cr or Al were prepared through solid-state methods. The room-temperature bulk Li⁺-ion conductivity is 1.63 × 10⁻⁴ S cm⁻¹ for the composition Li_1.25Cr_0.25Ti_1.5O₄. Addition of Li₃BO₃ (LBO) increases ionic and electronic conductivity reaching a bulk Li⁺ ion conductivity averaging 6.8 × 10⁻⁴ S cm⁻¹, a total Li-ion conductivity averaging 4.2 × 10⁻⁴ S cm⁻¹, and electronic conductivity averaging 3.8 × 10⁻⁴ S cm⁻¹ for the composition Li_1.25Cr_0.25Ti_1.5O₄ with 1 wt. % LBO. An electrochemically active solid solution of Li_1.25Cr_0.25Mn_1.5O₄ and LiNi_0.5Mn_1.5O₄ was prepared. This work proves that Li-stuffed spinels can achieve fast Li-ion conduction and that the concept is potentially useful to enable a single-phase fully solid electrode without interphase impedance.     

First-principles study of antiferromagnetic cobalt spinels

We report a comparative study of the electronic structure and magnetic properties of two cobalt compounds Co₃O₄ and Co₃S₄, through first-principles Hubbard-U calculations. Our results indicate that Co₃O₄ and Co₃S₄ have similarities in crystal structure (normal spinel), magnetic order (antiferromagnetism), Co spin configuration (high spin Co²⁺ and low spin Co³⁺), and comparable band-gap energy. However, the U-dependence on electronic structure in two materials are different from each other. With a change in the applied U values, the band dispersion and the type of band gap are significantly changed in Co₃O₄, while the band-gap energy only is affected in Co₃S₄.     

纳米尺度NiLa2O4尖晶石催化NaBH4还原亚胺制仲胺

由溶胶-凝胶法制得的Ni-La化合物经热分解制备了纳米尺度NiLa2O4尖晶石，在750 oC焙烧后形成了结晶良好的尖晶石结构.采用差热分析、X射线衍射、透射电镜、扫描电镜和粒度分布分析等手段表征了该尖晶石的物理化学性质.结果表明，该纳米颗粒有规则的外形和确定的晶面，由平均粒径为40 nm的规整半球晶粒组成.精修的晶胞参数a=3.861205?和c=12.6793?.在NaBH4选择还原亚胺制相应仲胺的反应中，该新型纳米NiLa2O4尖晶石可用作高效多相催化剂，得到了较高的产物产率.所有反应可在室温和相对较短的时间内完成.在优化的反应条件下，均可得到带有不同芳基的，包括带有吸电子和供电子基团的仲胺.该催化剂回收简便，重复使用4次，其催化活性未见明显下降.     

锂离子电池正极材料LiNi0.5Mn1.5O4金属掺杂的第一性原理研究

近来尖晶石相LiNi0.5Mn1.5O4被认为是一种有前景的二次锂离子电池正极材料.但是其相对较差的循环性能和倍率性能限制了LiNi0.5Mn1.5O4的大规模应用.金属掺杂被认为是一种提高其电化学性能的有效方法.然而,还急需深层次地理解掺杂对材料结构和电化学性质的影响.采用第一性原理方法,系统地研究了金属掺杂的LiM0.125Ni0.375Mn1.5O4(M为Cr,Fe和Co)电极体系的结构与电子性质.计算结果显示,少量的过渡金属M取代LiNi0.5Mn1.5O4晶格中的Ni,能够有效抑制材料在电化学脱嵌锂过程中的体积变化(从锂化相到脱锂相,体积变化率约为4%,而未掺杂的情况为4.7%),提高材料循环性能.体系态密度表明金属掺杂能够减小体系的带隙,进而提高材料的电子传导.另外,通过Li离子的扩散计算,我们发现与未掺杂的LiNi0.5Mn1.5O4相比,Co掺杂使得Li在材料中两条不同扩散路径的扩散能垒分别降低了约90 meV和140 meV,表明Co掺杂有利于Li在材料中的快速扩散.     

尖晶石铁氧体TixNi1-xFe2O4中阳离子分布和Ti离子磁矩的实验研究

采用固相反应法制备了系列样品Ti_xNi_1-xFe₂O₄ (x=0.0, 0.1, 0.2, 0.3, 0.4). 室温下的X射线衍射谱表明样品全部为(A)[B]₂O₄型单相立方尖晶石结构, 属于空间群Fd3m. 样品的晶格常数随Ti掺杂量的增加而增大. 样品在10 K温度下的比饱和磁化强度σ_S随着Ti掺杂量x的增加逐渐减小. 研究发现, 当Ti掺杂量x≥ 0.2时, 磁化强度σ随温度T的变化曲线出现两个转变温度T_L和T_N. 当温度低于T_N时, 磁化强度明显减小; 当温度达到T_N时, dσ/dT具有最大值. σ-T曲线的这些特征表明, 由于Ti掺杂在样品中出现了附加的反铁磁结构. 这说明样品中的Ti离子不是无磁性的+4价离子, 而是以+2和+3价态存在, 其离子磁矩的方向与Fe和Ni离子的磁矩方向相反. 利用本课题组提出的量子力学方势垒模型拟合样品在10 K温度下的磁矩, 得到了Ti, Fe和Ni三种阳离子在(A)位和[B]位的分布情况, 并发现在所有掺杂样品中, 80%的Ti离子以+2价态占据尖晶石结构的[B]位.     

Nitride Spinel: An Ultraincompressible High‐Pressure Form of BeP2N4

Owing to its outstanding elastic properties, the nitride spinel γ‐Si₃N₄ is of considered interest for materials scientists and chemists. DFT calculations suggest that Si₃N₄‐analog beryllium phosphorus nitride BeP₂N₄ adopts the spinel structure at elevated pressures as well and shows outstanding elastic properties. Herein, we investigate phenakite‐type BeP₂N₄ by single‐crystal synchrotron X‐ray diffraction and report the phase transition into the spinel‐type phase at 47 GPa and 1800 K in a laser‐heated diamond anvil cell. The structure of spinel‐type BeP₂N₄ was refined from pressure‐dependent in situ synchrotron powder X‐ray diffraction measurements down to ambient pressure, which proves spinel‐type BeP₂N₄ a quenchable and metastable phase at ambient conditions. Its isothermal bulk modulus was determined to 325(8) GPa from equation of state, which indicates that spinel‐type BeP₂N₄ is an ultraincompressible material.