Mn和Fe掺杂对尖晶石氧化物Co2MnO4结构和磁性的影响

以金属盐及柠檬酸为原料, 采用溶胶-凝胶法制备了尖晶石氧化物Co_2-xMn_1+xO₄和Co_2-xFe_xMnO₄系列, 通过XRD、FT-IR及PPMS等手段研究了Co₂MnO₄及系列掺杂样品的成相、结构、磁性等特征。结果表明, Co_2-xMn_1+xO₄系列在x<0.6时, 呈单相立方结构, 晶格常数和磁性随着Mn掺杂量的增加而增大, x≥0.6时逐渐向四方结构转化, 磁性下降, 并呈现磁化强度不易饱和的特征; Co_2-xFe_xMnO₄系列样品在x<1.75成分范围内均可保持立方结构, 且晶格常数和磁性都随着x增大而提高。这些变化主要是由于掺杂原子尺度及磁矩均大于原有元素, 掺杂后样品内部的磁性相互作用有所增强。     

Co3O4纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用

以Co(NO₃)₂·6H₂O为钴源, NH₄F和尿素作为添加剂, 通过水热法在粘胶基活性炭纤维(ACF)的表面生长了Co₃O₄纳米线, 制备了Co₃O₄@ACF复合材料并进行了结构形貌表征及电化学性能测试。结果表明: 针状的Co₃O₄纳米线阵列均匀地垂直生长在活性炭纤维表面, 形成了丰富的介孔结构。通过改变Co(NO₃)₂·6H₂O的用量, 可以获得不同负载量的Co₃O₄@ACF复合材料。当Co₃O₄负载量为47wt%时, Co₃O₄@ACF复合材料在1 A/g电流密度下的比电容高达566.9 F/g, 几乎是纯Co₃O₄的2倍; 在15 A/g的电流密度下, 其比电容仍可达到393.3 F/g, 表现了较好的倍率特性; 经过5000次循环充放电后, 其比电容仍可保持84.2%, 展现了优良的循环稳定性。     

Co2MnSi1-xZx(Z=B,P, As) Heusler合金的磁性和电子结构的第一性原理计算

通过第一性原理计算研究了Co₂MnSi_1-xZ_x(Z=B, P, As) Heusler合金的能带结构和自旋极化，同时也证明了具有不同价电子的其他元素Z对Si的取代可以控制费米能级在带隙中的移动。与此同时，随着同种Z元素浓度的变化，晶格参数具有接近线性变化的特征，并且这些合金的能带结构具有相似的特点。不同合金的磁矩随价电子数呈线性变化趋势，符合Slater-Pauling行为。由计算结果可知，当x=0.125左右，Co₂MnSi_1-xP_x和Co₂MnSi_1-xAs_x合金具有较好的电子性质和较高的自旋极化。     

氮化硼纳米管增强氮化硅复合材料的裂纹扩展阻力行为

用氮化硼纳米管(BNNT)增强氮化硅(Si₃N₄)陶瓷制备了BNNT/Si₃N₄复合材料, 利用三点弯曲强度及单边切口梁(SENB)法测定了BNNT/Si₃N₄复合材料的弯曲强度和断裂韧性。通过SEM观察了BNNT/Si₃N₄复合材料微观形貌。基于BNNT增强Si₃N₄陶瓷复合材料的裂纹扩展阻力计算公式, 构建了BNNT对Si₃N₄陶瓷裂纹屏蔽区的裂纹扩展阻力的数学模型。用该模型的计算结果与Si₃N₄陶瓷的裂纹扩展阻力进行了对比。结果表明: BNNT/Si₃N₄复合材料的弯曲强度和断裂韧性明显高于Si₃N₄陶瓷, 说明BNNT对Si₃N₄陶瓷的裂纹扩展有阻力作用, 摩擦拔出是Si₃N₄陶瓷抗裂纹扩展能力提高的主要原因; BNNT对Si₃N₄陶瓷有明显的升值阻力曲线行为。通过有限元模拟裂纹尖端应力分布, 发现BNNT使Si₃N₄陶瓷裂纹尖端的最大应力转移到纳米管上, 而且BNNT降低了Si₃N₄陶瓷裂纹尖端的应力, 对Si₃N₄陶瓷尖端的裂纹有屏蔽作用, 从而提高了Si₃N₄陶瓷的裂纹扩展阻力。     

镍掺杂四氧化三钴纳米线阵列的制备及其超级电容特性

采用直流电化学沉积与高温氧化相结合的合成方法, 在氧化铝模板的辅助下, 成功制备了一种新颖的Ni掺杂的Co₃O₄纳米线阵列, 利用X射线衍射仪、扫描电镜和高分辨透射电镜等对所制备的纳米线阵列的物相和形貌进行了表征, 结果表明：所制备的Ni掺杂Co₃O₄纳米线形貌和尺寸均匀、垂直于基底排列, 纳米线的平均直径约为80 nm, 长度约为1.4 μm, 整个纳米线由纳米颗粒堆积而成, 其中Co : Ni的比例约为20 : 1。利用循环伏安和恒流充放电技术在2 mol/L的KOH电解液中对材料的电化学性能进行了测试, 结果显示所制备的纳米线阵列具有优异的电化学电容特性, 当电流密度为10 mA/cm²时, 纳米线阵列的面积比电容为173 mF/cm², 经过1000次充放电后, 比电容值仍能保持最初值的98%, 表现出良好的循环稳定性。优异的性能可归因于材料的比表面积较大以及镍掺杂后材料导电特性的提高。     

四氧化三钴及掺杂材料电催化性能的研究进展

综述了Co₃O₄及掺杂材料的性质、结构和电催化性能。Co₃O₄中的钴离子是Co²⁺和Co³⁺的混合价。由于Co₃O₄具有独特的尖晶石晶体结构，有利于Co²⁺和Co³⁺离子之间的电子传导，具有空电子轨道且易实现晶格氧化可作为氧还原反应(ORR)催化剂。综述了Co₃O₄的电催化性能的影响因素主要由其表面积和电子态决定，表面积通过调整纳米结构的大小和形貌来调节，电子态可以通过掺入第三种元素或氧空位来调控。综述了Co₃O₄掺杂不同材料后均表现出优异的催化性能与良好甲醇耐受性。Co₃O₄与Pd掺杂可以提高金属Pd在载体表面的分散性，降低金属颗粒团聚；Co₃O₄与P的组合使催化剂的内在活性增强；Co_...     

Ni/Co3O4花状电极材料的合成及其电化学性能与第一性原理研究

通过水热法制备了一种单质镍掺杂Co₃O₄(Ni/Co₃O₄)的粉末，用伏安特性循环法研究了其电化学性能，同时根据第一性原理从原子尺度和电子结构的角度探究了Ni和Co₃O₄的掺杂机理。首先合成Ni/Co₃O₄粉末；其次对合成的材料结构及性能进行XRD和SEM表征分析，研究不同钴源及同一钴源不同钴镍比对制备的镍Ni/Co₃O₄形貌的影响；最后在不同缺陷和不同掺杂的影响下，建立准确的材料性能预测模型，揭示了修饰电极掺杂改性的微观机理。结果表明，不同钴源均制备出了花状形貌的Ni/Co₃O₄复合材料，电化学性能测试得到其比电容为670F/g;第一性原理计算所得掺杂机理，揭示了电化学修饰的Ni/Co₃O₄复合电极较大提高了材料的导电性能。     

纳米碳片负载Mott-Schottky型Co/Co9S8异质结的原位合成及电催化性能研究

以K₃[Co(CN)₆]为Co源,硫脲为S源,富含-OH和-NH₂的天然亲水性高分子壳聚糖为碳源,通过形成CS-K₃[Co(CN)₆]水凝胶将Co前驱体和S源均匀分布于C前驱体中。水凝胶形成的主要驱动力来自金属Co离子与壳聚糖中-NH₂的配位交联以及Co离子之间通过-CN的桥接作用。得益于均匀分散的前驱体和后续热解处理初期形成的Co的催化作用,通过简单地调控Co与S的原子比,原位构建出均匀镶嵌有Co/Co₉S₈异质结的N,S共掺杂富含微孔的碳纳米片(Co/Co₉S₈@N,S-CNSs)。采用SEM、TEM、BET、XRD、Raman、XPS和电化学工作站等方法对所制备催化剂的形貌、组成和结构以及电催化性能进行了表征。结果表明,形成的Mott-Schottky型Co/Co₉S₈异质界面有效地调控了活性中心的电子结构和电荷传输特性...     

石墨烯负载四硫化三钴复合物氧还原催化剂的制备与性能

选取二氯化钴和硫脲为钴源和硫源,以自制的还原氧化石墨烯(rGO)为载体,采用回流法在乙二醇溶剂中一步合成出Co₃S₄/rGO复合物。利用X射线衍射、扫描电镜和拉曼光谱(Raman)等手段对催化剂进行结构与形貌表征。结果表明:Co₃S₄/rGO样品中生成了具有立方结构的Co₃S₄细小晶粒,生长在rGO上的Co₃S₄晶粒发生聚集,具有较好的分散性。Co₃S₄/rGO的拉曼谱图的峰强比(I_D/I_G)为0.92,Co₃S₄对石墨烯结构无明显影响,石墨烯起到载体作用。在0.5mol/L H₂SO_4电解液中,线扫伏安测试表明,Co₃S₄/rGO催化剂具有良好的氧还原催化性能,氧还原起始电位为0.75V(vs.RHE),在动力学电位区,Tafel斜率和传递系数分别为119.5mV和0.49,氧分子在Co₃S₄/rGO催化剂上按四电子机理直接还原成水。     

掺杂Mg对纳米CoFe2O4/SiO2复合薄膜结构和磁性的影响

采用溶胶-凝胶旋涂法制备了纳米Co_1-xMg _xFe₂O₄/SiO₂(x = 0, 0.2, 0.4, 0.6, 0.8) 复合薄膜。利用XRD、SEM、原子力显微镜、振动样品磁强计对薄膜的结构、形貌和磁性进行了分析, 研究了Mg²⁺含量对样品结构和磁性的影响。结果表明, 样品中Co_1-xMg _xFe₂O₄具有尖晶石结构, 晶粒尺寸在38~46 nm之间。随着Mg²⁺含量的增加, Co_1-xMg _xFe₂O₄的晶格常数减小, 样品的饱和磁化强度减小, 矫顽力先增大后减小。样品Co_0.4Mg_0.6Fe₂O₄/SiO₂垂直和平行膜面的矫顽力分别为350.7 kA·m^-1和279.4 kA·m^-1, 剩磁比分别为67.2%和53.9%, Co_1-xMg _xFe₂O₄/SiO₂复合薄膜具有较明显的垂直磁各向异性。     

Changes in the real structure and magnetoresistance of Co90Fe10/Cu and Co90Fe10/Cu85Ag10Au5 multilayers after annealing

Annealing of the (1.1 nm Co₉₀Fe₁₀/2.2 nm Cu)×20 and (1.1 nm Co₉₀Fe₁₀/2.2 nm Cu₈₅Ag₁₀Au₅)×20 multilayers at 235 °C improved their magnetoresistance as compared to the virgin samples. Annealing at higher temperatures resulted in degradation of the magnetoresistance effect. This observation raised the motivation of a detailed structural study using small-angle X-ray scattering, wide-angle X-ray diffraction, electron diffraction and transmission electron microscopy with the aim to link the structural changes in the system to the changes in the magnetoresistance. The structure studies have shown that the maximum of the magnetoresistance observed after annealing at 235 °C is related to the separation of Co₉₀Fe₁₀ and Cu, which are partly intermixed at interfaces after the deposition process. The decay of the GMR effect at higher annealing temperatures is caused by an increase of the interface roughness, which led in the Co₉₀Fe₁₀/Cu multilayers to occurrence of non-continuous interfaces and to short-circuiting of magnetic layers. In the Cu₈₅Ag₁₀Au₅ multilayers, the combination of small-angle X-ray scattering and wide-angle X-ray diffraction has shown that Cu₈₅Ag₁₀Au₅ did not form an alloy with the nominal composition: Only a part of Au and Ag was dissolved in the copper structure; the remainder of Ag and Au formed precipitates.     

La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3钙钛矿高熵陶瓷粉体的制备及其电学性能

采用共沉淀法结合煅烧工艺制备La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃钙钛矿结构高熵陶瓷粉体, 显著降低了材料的合成温度。采用不同手段对其进行物相及形貌表征, 研究结果表明, 当煅烧温度为800 ℃时, 样品已经形成钙钛矿结构, 但有少量第二相; 当煅烧温度为1000 ℃时, La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃陶瓷粉体形成了纯钙钛矿结构。以La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃为电极材料制成工作电极, 采用三电极体系对工作电极进行电学性能测试, 包括循环伏安(CV)及恒流充放电(GCD)测试, 结果显示该电极材料在1 A/g电流密度下具有154.8 F/g的比容量;当电流密度增大到10 A/g时, 该电极材料仍然能保持初始比容量的47%(73 F/g), 说明La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃高熵陶瓷具有较好的倍率性能。     

EDTA辅助合成Co3O4纳米材料及其气敏性能

以有机化合物作为助剂合成纳米材料, 可调控材料的形貌和结构, 进而影响材料的催化和电化学性能。以乙二胺四乙酸二钠盐(EDTA-2Na)为助剂, 乙酸钴为钴源, 利用水热法合成Co₃O₄纳米材料, 测定材料的结构和气敏性能, 研究其结构与气敏性能的关系, 并探讨EDTA-2Na在材料合成中的作用机制。结果表明, Co²⁺与EDTA^2-形成的配合物调控Co₃O₄晶核的生长方向, 形成了边长约为50 nm的六边形介孔纳米片。在205 ℃下, 利用该材料构筑的气敏传感器对100×10^-6甲苯响应值约为104, 在225 ℃下对100×10^-6丙酮的响应值约为70。该传感器对甲苯和丙酮等挥发性有机化合物(VOCs)的高响应性能是由于EDTA-2Na辅助合成的Co₃O₄表面存在的大量缺陷, 提高了吸附氧含量。另外, 介孔结构和较大的比表面积有利于VOCs的吸附、表面反应和扩散。本研究提供了一种添加EDTA-2Na辅助合成Co₃O₄纳米材料并获得高响应VOCs气体传感器的有效方法。     

Perpendicular Magnetic Tunnel Junctions with CoFe/Pd Multilayer Electrodes and an MgO Barrier

We studied the magnetic and magnetoresistance characteristics of pseudospin-valve magnetic tunnel junctions (MTJs) based on CoFe/Pd multilayer electrodes with perpendicular magnetic anisotropy and an MgO barrier. The MTJs at annealing temperature (T _a) of 473 K showed a tunnel-magnetoresistance (TMR) ratio of 1.5%. An fcc (111)-oriented texture of the bottom and top Co₉₀Fe₁₀/Pd multilayer electrodes, together with an imperfectly crystallized MgO, were revealed by cross-sectional TEM images. The TMR properties of perpendicular MTJs with a Co₂₀Fe₆₀B₂₀ or Co₅₀Fe₅₀ layer inserted between the CoFe/Pd multilayer electrodes and the MgO barrier were also studied. The TMR ratio with Co₂₀Fe₆₀B₂₀ insertion was 1.7% at T _a= 473 K and monotonically decreased at T _a over 523 K. The TMR ratio with Co₅₀Fe₅₀ insertion increased up to 3% at T _a= 573 K and then decreased to 0.4% at T _a= 598 K. The influence of the Pd layer on CoFeB was studied by using the simplified structures of Pd/CoFeB/MgO/CoFeB/Pd and Ta/CoFeB/MgO/CoFeB/Ta with inplane anisotropy. A former structure with Pd resulted in reduced TMR ratio which decreases with increasing T _a, whereas MTJs with a Ta-based structure showed a monotonic increase of a TMR ratio. The low TMR ratio observed in Pd-containing structures appears to result from crystallization of CoFeB in an unfavorable crystal orientation.     

The (SmZr)Co$_3$Phase in Sm(CoFeCuZr)$_rm z$Magnets

Detailed microstructural characterization of magnets and homogenized as-cast alloys, which included X-ray diffraction Rietveld analysis, has indicated that the so-called platelet or lamellae phase is (SmZr)₁(CoFeCu)₃ with the PuNi₃ structure and lattice parameters a~0.5 nm and c~2.4 nm. The structural and magnetic properties of the (SmZr)Co₃ phase were investigated. The microstructure shows two phases differing in their Zr/Sm ratio. Magnetization curves for the samples (Sm_0.33Zr _0.67)Co₃, (Sm_0.33Zr_0.67)Co _2.97Fe_0.03, and (Sm_0.67Zr_0.33)Co₃ are consistent with the two-phase microstructure observed. Room temperature coercivity values of these samples are low (ap1 kOe.)     

Magnetic anisotropies in single and multilayered thin films grownby bowed-substrate sputtering

Thin-film structures composed of nearly nonmagnetostrictive single-layer Co₇₆Fe₄B₂₀ or magnetostrictive Fe₈₀B₂₀ and Co₇₅Si₁₅B₁₀ amorphous layers have been deposited on bowed glass substrates using the RF-sputtering technique. The fabrication procedure induces a postdeposition compressive stress in the thin-film structure when the sample is retrieved from an arching device in the sputtering chamber. This results in an induced magneto-elastic anisotropy that governs the magnetic easy axis of the film, depending on the sign of the magnetostriction constant of each layer. Particular attention is paid here to heterogeneous structures made of bi- or multilayers with magnetic easy axis oriented in a different direction in each layer. Bulk magnetic properties were evaluated from hysteresis loops and thermomagnetization measured by vibrating sample magnetometry (VSM) and quantum interference device (SQUID) magnetometry. Magnetic domain walls and out-of-plane magnetized domains were observed by a Kerr imaging system and magnetic force microscopy. The combination of microstructure and strains induced in the layers determines the orientation of the observed magnetic anisotropies, which vary from high in-plane anisotropies up to out-of-plane orientations for selected films. The results, which provide reassurance that effective anisotropies are induced in each of the layers, are discussed in terms of the interactions between magnetic phases with different induced easy magnetization axes