MnO2/NiCo2O4复合材料的控制合成及其电化学性能研究

采用两步合成法制备了MnO_2/NiCo_2O_4核壳结构纳米棒,使用场发射扫描电子显微镜、X射线衍射和电化学工作站研究了其形貌特征和电化学性能。研究结果表明,在α-MnO_2纳米棒上生长了均匀的NiCo_2O_4纳米片,这种核壳结构纳米棒所制备的电极在充放电电流密度为0.5A/g时比电容达到了434F/g,明显比纯α-MnO_2的比电容(256F/g)高,循环测试2 000次后,比电容保留量为91.8%,表现出了优秀的电化学性能,具有广阔的应用前景。     

Insertion/extraction reactions of lithium with LiV2O4

Lithium has been inserted into, and extracted from, the spinel Li_1.0V₂O₄ both electrochemically and chemically. Electrochemical and structural data show that in the system Li_1+xV₂O₄, for 0 < x ≤ 0.5, Li⁺ ions are inserted into the interstitial octahedral sites of the A_tet[B₂]_octX₄ spinel structure. At x ≈ 0.5, Li⁺ ions in the tetrahedral A-sites are displaced into the remaining octahedral sites to yield, at x = 1, a rocksalt phase Li₂V₂O₄; the [B₂]X₄ framework is unperturbed by the lithiation process. This framework also remains intact when Li⁺ ions are removed from Li_1.0V₂O₄ to a composition Li_0.67V₂O₄. Further extraction of lithium from the structure is accompanied by migration of some vanadium ions from the B-sites to the interstitial octahedral sites of the spinel structure. This process reduces the crystal symmetry from cubic to trigonal symmetry. In Li_0.27V₂O₄ the structure resembles that of Li_0.22VO₂, obtained by delithiation of layered LiVO₂, in which the vanadium cations are distributed in a 2:1 ratio between alternate cubic-close-packed oxygen layers; in the LiV₂O₄ spinel this ratio is 3:1.     

A neutron diffraction study of the ferrimagnetic spinel NiCo2O4

Neutron-diffraction experiments at 4.2K on a polycrystalline sample of the spinel NiCo₂O₄ prepared at 320°C revealed 92% occupancy of the tetrahedral (A) sites by cobalt and Neel ferrimagnetism with mean A-site and B-site moments 〈μ_A〉 = 2.29(9)μ_B and 〈μ_B〉 = ?0.97(13)μ_B. Diffuse scattering and electron microscopy demonstrated variations with position in the Ni/Co ratio. These and literature-magnetization data are interpreted with the assumption that the σ-bonding d orbitals form itinerant-electron states with overlapping energies for A-site Co²⁺ and B-site Ni²⁺ configurations. The formal valencies for these ions become low-spin Co_A^(3?δ)+ and Ni_B^(2+δ)+, where δ increases with externally applied field H.     

Fe3O4/MnO2磁性复合氧化物催化剂的制备及性能

具有磁性的非均相催化剂价格低廉、低污染、高能效、容易从溶液中分离出来。经过水热合成法合成的Fe₃O₄/MnO₂磁性复合氧化物催化剂在活化过一硫酸盐（2KHSO₅·KHSO₄·K₂SO₄）产生硫酸根自由基（SO₄-）降解水中有机污染物表现出了优良的性能。把不同质量的磁性Fe₃O₄微球与线状的MnO₂负载到一起,合成三种Fe₃O₄:MnO₂质量比分别为1:3、2:3、1:1的Fe₃O₄/MnO₂催化剂,经过XRD、SEM和TEM表征,表明这两种金属氧化物负载到一起。对比不同Fe₃O₄:MnO₂质量比的Fe₃O₄/MnO₂磁性复合氧化物催化剂活化2KHSO₅·KHSO₄·K₂SO₄的活性,发现Fe₃O₄/MnO₂（2:3）催化剂催化活性最高。通过考察不同因素对Fe₃O₄/MnO₂（2:3）催化活性的影响得出,水中罗丹明B（Rh B）降解的最佳条件为10 mg/L Rh B、0.4 g/L Fe₃O₄/MnO₂催化剂、0.3 g/L 2KHSO₅·KHSO₄·K₂SO₄、pH=8。Fe₃O₄/MnO₂（2:3）磁性复合氧化物催化剂经过3次循环利用后,催化活性没有明显下降。SO₄-在降解水中Rh B起主要作用。      

Magnetic properties of NiSb2O4

The magnetic transition of the antimony oxide NiSb₂O₄ has been studied using heat capacity measurements and magnetic susceptibility data. The Néel temperature previously evaluated from neutron diffraction is confirmed: T_N = 45 ± 1 K. The entropy excess ΔS(20 – 60 K) associated with the transition is calculated and compared with the theoretical value. The susceptibility data are interpreted in terms of a Curie-Weiss law (θ_p = − 98K, M_eff = 3.98 μ_ß). Exchange integrals are evaluated.     

Molten salt synthesis and thermoelectric properties of Ca2Co2O5

A molten salt method was applied to synthesize Ca₂Co₂O₅ powder by using Co₃O₄ and CaCO₃ as raw materials and CaCO₃-CaCl₂ as eutectic salt. The formation process and molten salt mechanism of Ca₂Co₂O₅ were investigated by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that sheet-like particles can be obtained at 963 K. Moreover, the electrical conductivity and the Seebeck coefficient of the specimen were measured from 323 to 963 K. The properties increased with increasing temperature and the highest value of power factor (2.0 × 10^− 4 W m^− 1 K^− 2) was obtained at 963 K, which indicates that molten salt synthesis is a promising method to prepare high thermoelectric performance material.     

硅元素掺杂改性尖晶石型锰酸锂的研究进展

尖晶石锰酸锂(LiMn₂O₄)具有理论比容量高、热稳定性高、价格低廉、循环性能良好等特点,深受研究者的亲睐,目前已有固相法、燃烧合成法和共沉淀等多种制备方法。为了进一步改善该材料的循环性能,研究者提出了元素掺杂的策略,元素掺杂改性是基于改变材料的晶体结构或材料中部分元素的平均价态来提高材料的电化学性能和结构的稳定性。Si⁴⁺掺杂可以取代材料中的部分Mn⁴⁺,从而使材料产生Jahn-Teller效应的离子数降低和尖晶石锰酸锂的八面体体积扩大,提高电化学性能。为此,综述了近几年来单一硅元素掺杂及硅与其他元素复合掺杂改性尖晶石型锰酸锂正极材料的研究进展。     

NiCo2O4/氧化石墨烯复合材料制备与电化学性能研究

为了研究NiCo₂O₄/氧化石墨烯(NiCo₂O₄/GO)复合材料的电化学性能,本文通过先水热合成前驱体再煅烧的方法制备了一系列NiCo₂O₄/GO复合材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学方法对其进行物理表征,其中以GO质量浓度为1 mg/mL悬浊液制备出的NiCo₂O₄ /GO-3复合材料呈类海胆状结构.在1 M KOH水溶液中使用循环伏安法、恒电流充/放电法和交流阻抗法研究了NiCo₂O₄/GO复合材料电化学性能.研究表明,与纯NiCo₂O₄相比,制备的NiCo₂O₄ /GO复合材料的比容量和赝电容性能均有明显提高,这主要是由于NiCo₂O₄ /GO复合材料中NiCo₂O₄与GO纳米片的相互作用形成的高孔隙率复合结构;NiCo₂O₄ /GO-3复合材料在电流密度为0.5~3.0 A/g时,比电容超过650 F/g,具有良好的倍率性能和高比容量.采用本文方法合成的NiCo₂O₄/GO复合材料,既提高了其倍率性能又保证了高比容量,是一种良好的超级电容器电极材料.     

Fe-doped NiCo2O4 hollow hierarchical sphere as an efficient electrocatalyst for oxygen evolution reaction

We prepared porous Fe-doped nickel cobaltate (Fe-NiCo₂O₄) hollow hierarchical nanospheres through a facile self-templated synthetic strategy. Due to the porous hollow structure and composition, the Fe-NiCo₂O₄ presented vastly superior electrocatalytic activity for the oxygen evolution reaction (OER), compared with NiCo₂O₄ and the majority of other OER catalysts. With an aim of stimulating a current density of 10 mA·cm⁻², the Fe-NiCo₂O₄ catalyst needs an overpotential of 210 mV, which is on a par with the general properties of commercial IrO₂. In addition, the Fe-NiCo₂O₄ catalyst performed stably in long-term testing. The excellent activity and long-term stability showed that such catalysts have great promise for widespread application in the field of water splitting.     

NiCo2O4纳米线/SiC复合纤维制备及其电化学性能

以正硅酸乙酯(TEOS)为硅源,聚乙烯吡咯烷酮(PVP)为助纺剂,采用静电纺丝结合碳热还原制备出结晶度较高的β-SiC纤维,其比表面积为92.6 m2/g,表现出双电层电容储能特征,比电容为155.7 F/g。然后,利用水热法在SiC纤维表面生长出大量直径约为15 nm的NiCo₂O₄纳米线,得到NiCo₂O₄纳米线/SiC复合纤维。测试表明,NiCo₂O₄纳米线/SiC复合纤维中镍和钴元素分别以Ni2+/Ni3+和Co2+/Co3+价态形式存在,由于NiCo₂O₄纳米线与SiC纤维的协同作用,NiCo₂O₄纳米线/SiC复合纤维比电容显著提高,并表现出双电层和赝电容并存的特征,比电容可达300.3 F/g,当功率密度为58.1 W/kg时,NiCo₂O₄纳米线/SiC复合纤维能量密度为60.1 W·h/kg。      

Feather-like NiCo2O4 self-assemble from porous nanowires as binder-free electrodes for low charge transfer resistance

The unique feather-like arrays composing of ultrathin secondary nanowires are fabricated on nickel foam (NF) through a facile hydrothermal strategy. Thus, the enhancement of electrochemical properties especially the low charge transfer resistance strongly depends on more active sites and porosity of the morphology. Benefiting from the unique structure, the optimized NiCo₂O₄ electrode delivers a significantly lower charge transfer resistance of 0.32 Ω and a high specific capacitance of 450 F·g⁻¹ at 0.5 A·g⁻¹, as well as a superior cycling stability of 139.6% capacitance retention. The improvement of the electrochemical energy storage property proves the potential of the fabrication of various binary metal oxide electrodes for applications in the electrochemical energy field.     

团簇NiCo2S4的磁学性能

为探究团簇NiCo₂S₄的磁学性能,本文依据密度泛函理论(DFT)在B3LYP/Lan12dz水平下对团簇NiCo₂S₄进行优化计算,确定了三重态下的6种优化构型,并从轨道成单电子数、自旋布居数、磁矩、自旋密度差、轨道态密度图多个角度对构型进行分析。研究表明:团簇NiCo₂S₄的6种构型中,构型2^{(3)性能最优异,而热力学稳定性最好的构型1(3)在磁学性能方面表现一般,其余构型磁学性能相近。对于团簇NiCo₂S₄的磁性强度,在原子轨道上,s、p轨道对团簇NiCo₂S₄整体的磁性强度贡献较小,d轨道对整体的磁性强度贡献最大;Ni原子和自旋向上的α成单电子是团簇整体磁性强度的主要贡献者,其中,s轨道成单电子数的主要贡献者是S原子,p、d轨道主要是金属原子,Ni原子d轨道主要受α成单电子影响,Co、S原子既受α成单电子的影响又受β成单电子的影响。团簇NiCo₂S₄作为磁性材料时采用构型2(3)}作为模型基础,可以通过增大金属Ni比例来增强磁性。     

Effect of FeOx loaded on CoOx/Al2O3 catalyst for the formation of thin-walled carbon nanotubes

Effects of FeO_x loaded on CoO_x/Al₂O₃ catalyst on the yield and morphology of the produced carbon nanotubes were studied. The findings showed that the addition of a small amount of FeO_x on the CoO_x/Al₂O₃ catalyst provoked the formation of carbon nanotubes with a thin wall structure. The results also revealed that an increase in FeO_x content decreased the yield of carbon nanotubes. An optimized weight ratio of CoO_x to FeO_x was found to be 8:2 (w/w) whereby the catalyst of this composition grew carbon nanotubes with a thin wall structure and not of diminutive carbon yield.     

Phase relations in the CaAl2O4|CaGa2O4 system

The solid state reactions and the phase relations in the CaAl₂O₄|CaGa₂O₄ system, of which both end-members have the stuffed tridymite structure, were examined by using three kinds of starting materials; A (CaCO₃ + (Al,Ga)₂O₃), B (CaAl₂O₄ + CaGa₂O₄) and C (CaCO₃ + Al₂O₃ + Ga₂O₃). In the starting material B, a very low rate of solid state reaction between CaAl₂O₄ and CaGa₂O₄ was found, which seemed to be due to very slow interchange of Al³⁺ and Ga³⁺ located in tetrahedra of this structure. In order to obtain the probable equilibrium phase relations, it was necessary to use the starting material A. In the present system, a new phase was found in a wide range of composition as a stable phase, which was supposed to have the same structure as so-called metastable phase of CaGa₂O₄ and different array of tetrahedra from either CaAl₂O₄ or CaGa₂O₄|I.     

低温固相反应工艺对NiFe_2O_4纳米粉体形貌的影响

为了改善NiFe2O4纳米粉体气敏性,采用低温固相反应法制备了不同形貌的NiFe2O4纳米粉体.以FeSO4·7H2O、NiSO4·6H2O和NaOH作为反应物,充分研磨制备前驱体,通过先抽滤后600℃热处理和先600℃热处理后抽滤制备了两种NiFe2O4纳米粉体,通过X射线衍射和扫描电镜考察了不同制备工艺对纳米晶粒尺寸及形貌的影响.XRD和SEM分析结果表明:两种制备工艺均能生成NiFe2O4尖晶石相.先抽滤后热处理制备的NiFe2O4纳米粉体颗粒尺寸约为80nm,颗粒呈立方体结构.而先热处理后抽滤制备的NiFe2O4纳米粉体,由于热处理过程中存在Na2SO4相,使得NiFe2O4纳米粉体颗粒呈圆形片状结构分布,颗粒尺寸为50nm,厚度约10nm.     

温度对燃烧包覆LiMn2O4/ZnO及其电性能的影响

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。     

Microwave-assisted synthesis of LiCoO2 and LiCo1−xGaxO2: Structural features,magnetism and electrochemical characterization

Nanocrystalline (between 30 and 40 nm) LiCoO₂ and LiCo_1−xGa_xO₂ (0 ≤ x ≤ 0.15) powders have been prepared by using a standard microwave furnace.     

Growth of La2Mo2O9 films on porous Al2O3 substrates by radio frequency magnetron sputtering

Synthesis conditions of La₂Mo₂O₉ thin film by radio frequency (RF) sputtering technique on Al₂O₃ ceramic substrates are studied. It is found that the deposition temperature and oxygen partial pressure are the most important factors for obtaining pure La₂Mo₂O₉ films. Varying both parameters, Mo-rich, stoichiometric, and Mo-deficient films are obtained. With increasing the La:Mo ratio, films become denser. A crust layer is observed on top of the Mo-rich and the Mo-deficient films. The formation of the La₂Mo₂O₉ phase is discussed with respect to the sputtering mechanism.     

不同碳源对纳米锌铝尖晶石合成及颗粒粒径的影响

以硝酸铝、硝酸锌和柠檬酸为原料,以炭黑和酚醛树脂为碳源,采用溶胶-凝胶法制备了纳米锌铝尖晶石粉体,研究了高温还原气氛下不同碳源对纳米锌铝尖晶石合成及颗粒粒径的影响,并以高温氧化气氛热处理、无碳引入的试样作对比。研究表明:在还原气氛下,引入碳源的试样在600℃热处理后,锌铝尖晶石峰不明显,主要是因为碳起空间位阻作用,阻碍了离子传质;800℃热处理后可合成锌铝尖晶石,且纳米颗粒尺寸较小(20~30nm);热处理温度升高至1 000℃时,纳米锌铝尖晶石颗粒尺寸变化不大,碳的空间位阻作用抑制了颗粒长大和烧结。与炭黑相比,酚醛树脂抑制锌铝尖晶石颗粒长大的效果更好,可能因为树脂碳化后呈玻璃态,空间阻隔作用更强。但热处理温度不低于1 200℃时,纳米锌铝尖晶石易被CO或C还原,锌以Zn(g)的形式逸出,只有α-Al2O3相。然而,在空气气氛下,600℃热处理后即可合成纳米锌铝尖晶石,但热处理温度从600℃升至800℃时,锌铝尖晶石颗粒长大较明显,颗粒尺寸从27.5nm增至54.6nm,并呈烧结状。     

不同锰源对尖晶石型锰酸锂性能影响的研究

分别以自制锰源和工业用电解二氧化锰为原料,采用固相合成法,将锰源和碳酸锂的混合物合成尖晶石型锰酸锂.通过扫描电子显微镜、X射线衍射的方法研究了不同锰源合成的尖晶石型锰酸锂之间形貌和结构的区别,通过电性能测试研究了不同锰酸锂对锂离子电池电性能的影响.结果表明：合成的锰酸锂都有良好的尖晶石型立方结构,以碳酸锰为原料的自制三...