LiAl0.03Mn1.97O4的流变相辅助微波合成以及电化学性能

采用一种特殊微波合成法,流变相辅助微波合成法,制备了结晶度好、纯度高的尖晶石相的锂离子电池正极材料LiAl_(0.03)Mn_(1.97)O_4。对其进行了XRD分析和SEM研究,并就结构、形貌与传统固相法制备的LiMn_2O_4、LiAl_(0.03)Mn_(1.97)O_4进行了比较。采用这种漉变相辅助微波合成法制备的LiAl_(0.03)Mn_(1.97)O_4具有优良的电化学性能,电化学性能测试表明,这种材料具有比较高的首次放电容量(115mAh/g)以及良好的可逆性、优异的循环性能,25次循环结束比容量几乎不变,保持在115mAh/g左右,衰减性得到很好的改善。     

复合金属氧化物Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4的锂离子交换性能研究

具有尖晶石型结构的化合物能够在插入大量替代离子改变自身锂和氧化学计量数的同时保持结构的稳定性,这种特性能够被用于离子交换研究,用来满足提取锂的需求。通过检测尖晶石型复合金属氧化物的饱和交换能力、分配系数等,可以确定其具体特性。本文利用共沉淀/固相反应热结晶方法,合成尖晶石型复合金属氧化物Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4。实验结果表明,经酸化的Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4,其Mg~(2+)的抽出比率高达72%,Mn~(4+)和Ti~(4+)的溶解比率低于8.2%。实验分析表明,无机离子交换剂Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4对Li~+有较好的离子筛效应,离子选择性较好,酸化后的样品对Li~+的离子交换能力高达10.6mmol·g~(-1)。     

核壳结构的5V正极材料微球合成与改善的电化学性能

本文采用多步骤合成路线,分别制备了具有实心、空心和核壳结构的5 V LiNi_(0.5)Mn_(1.5)O_4正极材料微球.同时利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)和红外光谱(FTIR)等分析手段研究了上述材料的结构特征.其中SEM和TEM证实了所制备的镍锰尖晶石微球具有实心、空心和核壳结构.电化学性能测试进一步表明,核壳结构的LiNi_(0.5)Mn_(1.5)O_4正极材料在55℃条件下表现出良好的循环稳定性和优异的倍率性能,在8 C倍率下依然有98 mAhg~(-1)的放电比容量.其改善的电化学性能源于独特的核壳微观结构,不仅可以提高结构的稳定性,而且可以缩短锂离子的扩散路径.     

O2结构Liy[Mn1—xMx]O2（M＝Cr，Mg）的合成及结构研究

由高温焙烧法制备层状前驱体Na_(2/3)[Mn_(1-x)M_x]O_2（M＝Cr, Mg），再 经离子交换反应得到层状O2结构产物Li_y-[Mn_(1-x)M_x]。XRD表明Li_y[Mn_(1-x) M_x]O_2属六方晶系，P3ml空间群。Cr的添加量对前驱体的晶体结构有很大影响： 随着x值的增大，前驱体逐渐由层状P2结构Na_(2/3)[Mn_(1-x)Cr_x]O_2向正交结构 Na_4Mn_90_(18)转变。由SEM可以看到样品Li_y[Mn_(1-x)Cr_x]-O_2(x≤0.05)具有 六方层状结构。XPS分析结果表明样品Li_y[Mn_(0.95)Cr_(0.05)]O_2表面上的Mn和 Cr分别以Mn~(4+)存在，并且表面中Cr相对含量高于体相，而样品Li_y[Mn_(0.90) Mg_(0.10)]O_2的表面Mn和Mg分别以Mn~(4+)和Mg~(2+)存在，Mg/Mn比在表面与体相 基要一致。     

钴掺杂Sr1.5La0.5MnO4的合成及高温电化学性能研究

采用EDTA-柠檬酸法合成了中温固体氧化物燃料电池阴极材料Sr_(1.5)La_(0.5)Mn_(1-x)Co_xO_4(SLMCOx),并利用粉末X射线衍射(XRD)、X射线光电子能谱(XPS)以及电化学交流阻抗谱(EIS)进行表征。结果表明,该材料与Ce0.9Gd0.1O1.95(CGO)在1 200℃烧结12 h不发生化学反应。随着Co掺入量的增加,氧化物中Mn~(3+)和Co~(2+)含量增多,晶格氧含量降低,晶格畸变率增大。交流阻抗谱(EIS)测试结果显示,钴的掺杂明显降低电极的极化电阻,其中Sr_(1.5)La_(0.5)Mn_(0.7)Co_(0.3)O_4阴极在700℃空气中的极化电阻为0.62Ω·cm~2,明显小于Sr_(1.5)La_(0.5)MnO_4阴极在750℃的极化电阻(1.5Ω·cm~2),表明钴掺杂的Sr_(1.5)La_(0.5)Mn_(1-x)CoxO_4是一种潜在的IT-SOFC阴极材料。     

单分散NixZn1-xFe2O4纳米颗粒的制备及其磁热效应

以乙酰丙酮金属盐为前驱体,三乙二醇为溶剂,采用多元醇法制备了镍锌不同配比的Ni_xZn_(1-x)Fe_2O_4(x=0,0.3,0.5,0.7和1.0)铁氧体,并通过X射线衍射仪(XRD),透射电子显微镜(TEM)和振动样品磁强计(VSM)等对样品的结构、形貌、磁性能和磁热性能进行了表征。结果表明:Ni_xZn_(1-x)Fe_2O_4铁氧体分散性较好,尺寸均一,形状近似球形,平均粒径为4~5 nm。Ni_xZn_(1-x)Fe_2O_4纳米颗粒在室温下表现出亚铁磁性,饱和磁化强度随着镍含量的增加先增大后减小,当x=0.5时达到最大值29.38 emu·g~(-1)。在382k Hz交变磁场作用下,Ni_(0.5)Zn_(0.5)Fe_2O_4铁氧体温度可升温至313 K,表现出较好的磁热性能。     

5V锂离子电池正极材料LiNi_(0.5)Mn_(1.5)O_4的低温燃烧法合成及性能研究

以IANO_3、Ni(NO_3)_2·6H_2O、Mn(NO_3)_2和CO(NH_2)_2为原料,采用低温燃烧法成功合成了5V锂离子电池正极材料LINi_(0.5)Mn_(15)O_4.通过XRD、SEM、循环伏安和恒电流充放电实验对合成样品进行了表征.结果表明,在850℃合成的正极材料LiNi_(0.5)Mn_(1.5)O_4具有立方尖晶石结构,规则的八面体晶形,粒度适中,比较均匀.合成产物具有良好的电化学性能,其充放电电压平稳,放电平台高达4.7V,4V放电平台几乎消失;放电容量达到124.92mAh/g,50次循环后放电容量仍可达到120.84mAh/g.     

富锂正极材料xLi_2MnO_3·(1-x)LiNi_(0.5)Mn_(0.3)Co_(0.2)O_2的制备及其电化学性能研究

本文利用共沉淀法制备了富锂材料xLi_2MnO_3·(1-x)LiNi_(0.5)Mn_(0.3)Co_(0.2)O_2(0.3≤x≤0.7),并进行了X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM)和恒电流充放电测试。研究了在一定的反应温度下合成出的材料的电化学性能。结果表明,Li_(1.17)Mn_(0.48)Ni_(0.25)Co_(0.1)O_2在0.1 C下的放电比容量为240.3m Ah·g~(-1),其在1 C倍率下100次循环后的比容量为180.6 m Ah·g~(-1),容量保持率为89.4%.     

CuO修饰的Cu_(1.5)Mn_(1.5)O_4尖晶石型复合氧化物对CO氧化的协同催化

铜锰复合氧化物是常用的氧化反应催化剂,一般认为铜锰尖晶石是活性组分;同时氧化铜和氧化锰也具有催化活性,但性能较差。研究表明,发现Cu_(1.5)Mn_(1.5)O_4和CuO的协同效应能促进CO的催化氧化。催化剂以柠檬酸络合法制备,采用氮气吸附-脱附、XRD、H_2-TPR、TEM、CO-TPD和O_2-TPD等手段对系列催化剂进行了表征,测试了对CO氧化的催化性能。结果表明,CuO修饰的Cu_(1.5)Mn_(1.5)O_4具有最好的催化性能和最高的单位表面活性(以单位表面积CO转化率计),表明CuO与Cu_(1.5)Mn_(1.5)O_4存在协同作用。认为协同作用源自CuO活化的O_2和Cu_(1.5)Mn_(1.5)O_4活化的CO结合生成CO_2提高了活性。     

用新型的半固相方法合成掺钴尖晶石材料LiCo_xMn_(2-x)O_4及其性能研究

用一种新型的半固相法合成得到LiCo_xMn_(2-x)O_4材料,通过X射线衍射技术 和充放电实验对材料的结构及循环性能进行了研究。与传统的固相合成法相比,这 种半固相法显示了产物颗粒尺寸均匀,电化学性能良好的特点。通过对结构,组成 与电化学性能关系的探讨,对不同半固相法合成路线的选择及适当的优化,可得到 电化学性能良好的掺钴尖晶石材料,其中LiCo_(0.016)Mn_(1.984)O_4在室温下的 初始容量为118 mA·h/g,循环25周后,容量仍能保持在113 mA·h/g左右。通过这 种新型合成方法得到的掺钴尖晶石材料,在高温下也表现出了令人满意的充入电循 环性能。     

Thermodynamic properties of spinel MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: A mass spectrometric study

The activities of oxides in stoichiometric spinel MgAl₂O₄ in the temperature range 1851–2298 K were determined from the data obtained by the Knudsen effusion mass spectrometry. The resulting Gibbs energies of spinel formation from simple oxides, the enthalpies and entropies of spinel formation from simple oxides (–12.02 ± 1.14 kJ/mol and 5.03 ± 0.56 J/(mol K), respectively), and the spinel melting enthalpy (55.81 ± 4.62 kJ/mol) satisfactorily agree with the available thermodynamic data.     

Zn-Fe尖晶石型复合氧化物催化分解N2O

用共沉淀法制备了Zn-Fe尖晶石型复合氧化物催化剂,用于有氧气氛中N₂O的分解反应;考察了复合氧化物的组成、焙烧温度及K改性对其催化活性的影响,并用氮气吸附、XRD和H₂-TPR等技术对催化剂结构进行了表征。结果表明,Zn-Fe尖晶石型复合氧化物具有良好的催化N₂O分解的活性;在优化出的Zn_0.8Fe_0.2Fe₂O₄-400催化剂上500℃下连续反应10 h时,有氧无水和有氧有水条件下N₂O转化率分别达到63.5%和22.2%。K改性Zn-Fe尖晶石型复合氧化物的催化活性均不及纯Zn-Fe氧化物,这是由于K改性催化剂的比表面积显著降低,而且K粒子迁移至催化剂表面,抑制了FeO_x的还原和表面氧物种的脱除。     

尖晶石CuM2O4(M=Al、Fe、Cr)催化甲醇重整反应的特性

采用柠檬酸络合法,经900 ℃热处理制备了CuAl₂O₄、CuFe₂O₄和CuCr₂O₄三种尖晶石,并进行了甲醇重整性能评价。结合XRD、H₂-TPR、SEM和BET等表征,研究了铜基尖晶石的催化特性。结果表明,三种铜基尖晶石的形貌和大小有极大差异,表现出不同的催化性能,CuAl₂O₄尖晶石获得最优的稳定性和最低的CO选择性,CuFe₂O₄尖晶石上CO选择性最高且稳定性差,CuCr₂O₄尖晶石上石墨碳沉积最严重。根据长时间评价结果和表征数据发现,在反应气氛中铜基尖晶石不稳定,通过释放活性铜而起催化作用;同时铜的烧结长大与积炭现象共同影响催化性能。     

掺钛尖晶石锂锰氧化物的合成、结构及电化学性能研究

以掺钛电解二氧化锰为锰源合成了一系列掺钛尖晶石锂锰氧化物样品.实验结果表明,无论是在新制样品40次循环的充放电实验中,还是在经过40次循环充放电并在放电状态下贮藏3个月的再次充放电实验中,掺钛样品均具有极好的电化学性能.600℃掺钛样品在第一循环中的放电容量达到206mA·h/g.在放电态贮藏3个月后,再次充放电实验中,第一循环的放电容量达到144mA·h/g.XRD分析表明,掺钛样品仍然具有立方结构.还用红外和拉曼光谱技术研究了钛对尖晶石锂锰氧化物的电化学性能的改善作用.     

Preparation of Magnesium,Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents

Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel‐type ferrite nanoparticles MFe₂O₄ (M=Mg, Zn, Co, Ni). The best results for phase‐pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid‐phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase‐pure spinel‐type ferrite particles are thoroughly characterized by X‐ray diffraction, diffuse‐reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides.     

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.     

Cyano‐Bridged Trimetallic Coordination Polymer Nanoparticles and Their Thermal Decomposition into Nanoporous Spinel Ferromagnetic Oxides

The synthesis of a novel family of cyano‐bridged trimetallic coordination polymers (CPs) with various compositions and shapes has been reported by changing the compositional ratios of Fe, Co, and Ni species in the reaction system. In order to efficiently control the nucleation rate and the crystal growth, trisodium citrate dihydrate plays an important role as a chelating agent. After the obtained cyano‐bridged trimetallic CPs undergo thermal treatment in air at three different temperatures (250, 350, and 450 °C), nanoporous spinel metal oxides are successfully obtained. Interestingly, the obtained nanoporous metal oxides are composed of small crstalline grains, and the grains are oriented in the same direction, realizing pseudo‐single crystals with nanopores. The resultant nanoporous spinel oxides feature interesting magnetic properties. Cyano‐bridged multimetallic CPs with various sizes and shapes can provide a pathway toward functional nanoporous metal oxides that are not attainable from simple cyano‐bridged CPs containing single metal ions.     

Mn−O Covalency Governs the Intrinsic Activity of Co‐Mn Spinel Oxides for Boosted Peroxymonosulfate Activation

Transition metal (TM)‐based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot fully explain the efficient TM redox cycling. Here, we discover a critical role of TM?O covalency in governing the intrinsic catalytic activity of Co_3?xMn_xO₄ spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn?O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor Mn_Oh–PMS interaction. With appropriate Mn^IV/Mn^III ratio to balance PMS adsorption and Mn^IV reduction, the Co_1.1Mn_1.9O₄ exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.     

Highly water-soluble nanocrystal powders of magnetite and maghemite coated with gluconic acid: Preparation, structure characterization, and surface coordination

A simple method was developed to prepare highly water-soluble nanocrystal powders of magnetic iron oxides with different oxidation degree from magnetite (Fe(3)O(4)) to maghemite (γ-Fe(2)O(3)) coated with gluconic acid (GLA). X-ray diffraction and transmission electron microscopy measurements show that the products have a narrow size distribution, and the cores are inverse spinel iron oxides and completely crystallized. Vibrating sample magnetometry measurements reveal that all the samples exhibit superparamagnetic behavior at room temperature. Fourier transform infrared (FTIR) and Raman spectra were used to identify the products. It is shown that GLA molecules are immobilized on the nanoparticle surface by chemical bonding and the carboxyl is asymmetrically bound to the surface iron atom, and the vacancies in the γ-Fe(2)O(3) cores are disordered. Compared with FTIR, Raman spectrum analysis is a rapid, simple, and accurate method for identifying inverse spinel iron oxides. The chemical stability and the high solubility of the products are explained in terms of the proposed coordination modes of the surface iron atom with GLA.     

Spinel–rocksalt transition as a key cathode reaction toward high-energy-density magnesium rechargeable batteries

Mg-metal-anode rechargeable battery (MRB) has been a promising candidate for next-generation batteries with high energy densities and high safety. The lack of high-performance cathode materials, however, retards the development of MRBs. In recent years, it has been revealed that various spinel oxides can accommodate a large amount of Mg, exhibiting relatively high potentials (2–3 V vs. Mg²⁺/Mg) and high capacities (～150 mAh g^?1) accompanied by the coherent structural transformation into the rocksalt structure. This review summarizes the recent progress in the development of such spinel–rocksalt transition materials from the viewpoints of the reaction mechanisms, design guidelines of spinel oxides (for tailoring the redox potential, volume change, and cyclability), and challenges to construct full-cell MRBs.