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.     

NiCo2O4/C复合电极材料的制备以及超级电容性能

采用化学共沉淀法合成了纳米级NiCo2O4/C复合材料,并以X射线衍射(XRD)、扫描电镜(SEM)对样品进行了结构和形貌的表征,结果表明,合成的复合材料为立方尖晶石结构,其粒径大小为30～40nm,颗粒呈球形且分布均匀。循环伏安(CV)、恒电流充放电测试表明,NiCo2O4/C复合材料在6mol/LKOH水系电解液中表现出优异的超级电容特征,在0～0.9V的电位范围内,NiCo2O4/C电极材料比电容量可高达290.49F/g,并具有良好的可逆性和优异的循环性能。     

Facile solvothermal synthesis of NiFe2O4 nanoparticles for high-performance supercapacitor applications

We report a green and facile approach for the synthesis of NiFe₂O₄ (NF) nanoparticles with good crystallinity. The prepared materials are studied by various techniques in order to know their phase structure, crystallinity, morphology and elemental state. The BET analysis revealed a high surface area of 80.0 m²·g⁻¹ for NF possessing a high pore volume of 0.54 cm³·g⁻¹, also contributing to the amelioration of the electrochemical performance. The NF sample is studied for its application in supercapacitors in an aqueous 2 mol·L⁻¹ KOH electrolyte. Electrochemical properties are studied both in the three-electrode method and in a symmetrical supercapacitor cell. Results show a high specific capacitance of 478.0 F·g⁻¹ from the CV curve at an applied scan rate of 5 mV·s⁻¹ and 368.0 F·g⁻¹ from the GCD analysis at a current density of 1 A·g⁻¹ for the NF electrode. Further, the material exhibited an 88% retention of its specific capacitance after continuous 10000 cycles at a higher applied current density of 8 A·g⁻¹. These encouraging properties of NF nanoparticles suggest the practical applicability in high-performance supercapacitors.     

La2O3添加对MgAl2O4-CaAl4O7-CaAl12O19复合材料烧结行为的影响

为适应材料轻量化的发展需要,在1 400~1 600℃温度下开发了MgAl₂O₄-CaAl₄O₇-CaAl₁₂O₁₉（MA-CA₂-CA₆）复合材料,并考察了La₂O₃添加对该复合材料烧结行为、显微结构和力学性能的影响。结果表明,La₂O₃添加剂优先固溶到MA-CA₂-CA₆复合材料组成晶相CA₆中,促使CA₆相发生晶格畸变,有效抑制了CA₆晶粒沿基面的异常长大,其形貌由片状向等轴状趋势转变,促使MA-CA₂-CA₆复合材料制备过程中由于CA₆晶粒异常长大而导致的多孔网状显微结构得以有效消除,因此也极大地改善了Mg²⁺的扩散条件,在一定程度上间接促进了MA晶粒的发育,有效促进了MA-CA₂-CA₆复合材料的烧结。经1 200℃预烧、1 600℃保温2 h烧成后,当La₂O₃的添加量为4wt%时,MA-CA₂-CA₆复合材料试样的显气孔率由19.2%下降至6.1%,体积密度由2.78 g/cm³上升至3.18 g/cm³,制得了MA、CA₂、CA₆晶相呈现交织分布、显微结构致密、有利于其力学性能改善的La₂O₃/MA-CA₂-CA₆复合材料,经1 200℃预烧、-1 600℃保温2 h烧成后的4wt% La₂O₃添加试样,其冷态抗压强度由317 MPa增加到了501 MPa。     

基于低温原位法制备Ga2O3或In2O3电子收集层的高效有机太阳电池

有机太阳电池(OSCs)中,温和的界面材料制备工艺对于拓宽材料适用范围和提高器件能量转换效率(PCE)具有重要作用.本文提出了简便易行的In₂O₃和Ga₂O₃电子收集层的制备方法,即旋涂In(acac)3和Ga(acac)3异丙醇前驱体溶液并结合低温热退火.在基于PM6:Y6的OSCs中引入In₂O₃和Ga₂O₃电子收集层,得到了性能优异的器件, PCE分别达到16.17和16.01.对比研究发现, In₂O₃的功函数WF为4.58 eV,这比WF为5.06 eV的Ga₂O₃更有利于与ITO电极形成欧姆接触,因此基于前者的器件开路电压更高.此外,电化学阻抗谱EIS的研究进一步揭示了In₂O₃和Ga₂O₃对器件内部电荷转移过程的影响及其性能差异的由来:In₂O₃的串联电阻损耗虽然较低,但Ga₂O₃的复合电阻较高,所以一定程度上提高了基于Ga₂O₃的器件的填充因子,进而补偿了其串联电阻的损失.本论文的对比研究发现, In₂O₃和Ga₂O₃都是OSCs优异的电子收集层.     

Three-dimensional sea urchin-like MnCo2O4 nanoarchitectures on Ni foam towards high-performance asymmetric supercapacitors

To construct supercapacitors (SCs) with high-efficient electrochemical properties, the morphology and structure of applied electrode materials are the key factors. Herein, three-dimensional (3D) sea urchin-like MnCo₂O₄ nanoarchitectures grown on Ni foam (NF) were successfully synthesized via a simple solvothermal method and subsequent annealing treatment. Electrochemical tests revealed that the area specific capacitances of the MnCo₂O₄ electrode and the corresponding assembled asymmetric device can achieve 1634 and 522 mF·cm⁻², respectively. When the power density of the assembled asymmetric supercapacitor (ASC) is 2.25 mW·cm⁻², the maximum energy density can reach 0.163 mW·h·cm⁻². After 5500 cycles of long-term stability test, the capacity retention rate maintains 91.7%. The excellent electrochemical performance can be mainly ascribed to the unique nanostructure of the material, which provides a great quantity of electroactive sites for Faraday redox reactions as well as accelerates the process of the ions/electrons transport. This work provides a certain reference value for the preparation of MnCo₂O₄ electrode with novel structure and excellent electrochemical performance for SCs.     

高镍LiNi0.8Co0.1Mn0.1O2的锂离子导体Li3PO4的包覆改性及电化学性能研究

采用典型的溶胶-凝胶法,在高镍LiNi_0.8Co_0.1Mn_0.1O₂正极颗粒表面包覆不同含量的Li₃PO₄锂离子导体。利用X射线衍射仪,扫描电镜对Li₃PO₄包覆前后的LiNi_0.8Co_0.1Mn_0.1O₂样品的晶体结构和微观形貌进行分析。结果表明,合成材料的层状结构明显,阳离子混排度低,并且Li₃PO₄成功包覆在LiNi_0.8Co_0.1Mn_0.1O₂颗粒表面。另外,对4个样品进行了首次充放电,倍率放电和循环性能比较,结果表明经过Li₃PO₄包覆后的正极材料的综合电化学性能明显比未包覆样品优越。首次库伦效率从未包覆样品的84.2%提高到2%(质量分数)Li₃PO₄包覆样品的89.2%。而且在5C高倍率,2%(质量分数)Li₃PO₄包覆LiNi_0.8Co_0.1Mn_0.1O₂的放电比容量是129.7 mAh/g,远远高于未包覆样品的92.6 mAh/g。同时,在常温和高温环境下循环100次后,2%(质量分数)Li₃PO₄包覆LiNi_0.8Co_0.1Mn_0.1O₂的容量保持率比未包覆样品分别高出7.1%和9.9%。     

锐钛矿型TiO2 / MnFe2O4 核壳结构复合纳米颗粒的制备及其光催化特性

采用柠檬酸盐前驱体技术, 合成了粒径约为20～70 nm 的尖晶石结构MnFe₂O₄ 纳米颗粒, 用聚乙烯亚胺( PEI) 对MnFe₂O₄ 纳米颗粒进行表面处理后, 以异丙醇钛为前驱物, 采用sol2gel 法在纳米MnFe₂O₄ 表面包覆锐钛矿型TiO₂ 纳米层形成核壳结构。利用透射电子显微镜( TEM) 、X射线衍射仪(XRD) 和振动样品磁强计等测试手段对样品的结构、形貌、粒径以及磁学性能等进行了表征。采用罗丹明B 的光催化降解反应对所制催化剂的活性进行了评价。结果表明, 核壳结构TiO₂ / MnFe₂O₄ 复合纳米颗粒的光催化活性随着壳层厚度的增加而增强,当达到一定厚度以后, 其催化活性不随壳层厚度的增加而改变。复合颗粒中TiO₂ 含量达到30 wt % , 反应时间4 h时, TiO₂ / MnFe₂O₄ 磁性光催化剂对罗丹明B 的光降解率达到100 % , 与纯TiO₂ 纳米粉体的催化活性相当, 且光催化活性稳定, 是一种便于回收、可重复使用的高效光催化剂。      

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.     

Preparation and properties of NiFe2O4 nanowires

Polycrystalline NiFe₂O₄ nanowires have been synthesized by PEG assisted co-precipitation method. The formation mechanism of the nanowires proposed is by means of the orientational aggregation of individual nanoparticles. X-ray diffraction, high resolution scanning electron microscopy, transmission electron microscopy, microRaman and vibrating sample magnetometry studies were carried out. The results show that NiFe₂O₄ nanowires were in polycrystalline form with diameter of 58 nm. The synthesized nanowires show room temperature ferromagnetic property with high coercivity. This method is expected to be useful for large scale synthesis of NiFe₂O₄ nanowires for the application of magnetic recording.     

CoFe2与CoFe2O4质量比及MgO稀释对CoFe2@CoFe2O4磁性的影响

采用金属有机盐热分解方法制备了MgO包覆的CoFe₂O₄纳米粒子（CoFe₂O₄@MgO）,然后将CoFe₂O₄@MgO在H₂中还原,接着在空气中氧化制备了一组CoFe₂@CoFe₂O₄@MgO样品;用盐酸溶液溶解CoFe₂@CoFe₂O₄@MgO中的MgO获得另一组样品（CoFe₂@CoF₂O₄）。测量并绘制了CoFe₂@CoFe₂O₄@MgO和CoFe₂@CoF₂O₄的磁化强度随外磁场及温度变化的关系曲线。随着氧化温度升高,CoFe₂@CoFe₂O₄@MgO和CoFe₂@CoF₂O₄的矫顽力H_c、饱和磁化强度M_s、剩磁比M_r/M_s及磁有序状态发生显著变化,这些变化强烈依赖于磁性粒子的各向异性及粒子间的偶极相互作用。     

Synthesis of Bi2Fe4O9 via PVA sol-gel route

Bi₂Fe₄O₉ powders were synthesized by a sol-gel process using polyvinyl alcohol (PVA) as a complexing agent. Differential scanning calorimetry (DSC), thermogravimetric (TG), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and Field emission scanning electron microscope (FSEM) techniques were used to characterize precursor and derived oxide powders. The effect of the ratios of positively charged valences to hydroxyl groups of PVA (Mⁿ⁺/-OH) on the formation of Bi₂Fe₄O₉ was investigated. XRD analysis showed that single-phase Bi₂Fe₄O₉ was obtained from the Mⁿ⁺/-OH = 2:1 and Mⁿ⁺/-OH = 1:1 precursors at the temperature of 700 °C. For the precursor with Mⁿ⁺/-OH = 4:1, pure Bi₂Fe₄O₉ formed at the temperature of 800 °C. Bi₂Fe₄O₉ powders clacined at 700 °C from Mⁿ⁺/-OH = 2:1 precursor shows weak ferromagnetism.     

表面活性剂对固相反应制备钴酸镍形貌影响的研究

采用醋酸镍、醋酸钴和草酸，加入不同的表面活性剂，在室温条件下进行固相化学反应，于60℃水浴恒温2d，获得前驱物；经热分析后，610℃分解．用XRD、SEM对热分解产物进行表征，获得了多种不同微观形貌的NiCo2O4复合氧化物．进行了不同聚合度和不同类型的表面活性剂对多种制备体系产物形貌影响的对比实验．实验结果表明，表面活性剂在合成过程中充当了软摸板剂，对产物形貌的构成产生了明显作用．     

ZrO2 (Y2O3) 增韧的氮化硅烧结体的性能及相关系

在高温(1400℃) 超高压(4. 2GPa) 下制备Y₂O₃ 部分稳定的ZrO₂ 增韧的氮化硅烧结体, 通过XRD 及机械性能测试等方法分析ZrO₂ 的相结构, 研究氮化硅烧结体的增韧机理。结果表明, 烧结体中加入少量的铝粉, 可提高t2ZrO₂ 的相变能力, 达到利用部分稳定的ZrO₂ 增韧氮化硅烧结体的目的。稳定剂Y₂O₃ 在ZrO₂ 中含量小于2. 5mol% 时, t→m 相变量及断裂韧性随Y₂O₃ 含量增加而逐渐提高, 韧性提高来源于相变增韧和微裂纹增韧; Y₂O₃含量大于2. 5mol% 时, t 相接近100% , 韧性主要来源于相变增韧, 增韧效果随Y₂O₃ 含量增加而逐渐减弱。Y₂O₃ 作为良好的烧结助剂, 促进氮化硅烧结体在超高压下致密化, 烧结体的硬度随Y₂O₃ 含量增加逐渐提高。      

Enhancement of Er I13/2 population in Y2O3 by energy transfer to Ce

We report measurements of the energy transfer between Er³⁺ and Ce³⁺ in Y₂O₃. The transition between the Er^{3+ 4}I_11/2 and ⁴I_13/2 excited states can be stimulated by energy transfer to Ce³⁺, augmenting the population in the ⁴I_13/2 state at the expense of that in the ⁴I_11/2 state. Experiments were performed on Y₂O₃ planar waveguides doped with 0.2 at.% erbium and 0–0.42 at.% cerium by ion implantation. From measurements of Er³⁺ decay rates as a function of cerium concentration we derive an energy transfer rate constant of 1.3×10⁻¹⁸ cm³/s. The efficiency of the energy transfer amounts to 0.47 at 0.42 at.% cerium. The energy transfer rate constant measured in Y₂O₃ is two times smaller for Er³⁺→Ce³⁺ than that for Er³⁺→Eu³⁺ in the same material.     

苯胺-SrTi(C2O4)2颗粒制备及其电流变性能

用沉淀法制备了苯胺-草酸氧钛锶（SrTi（C₂O₄）₂）颗粒。FTIR分析表明,苯胺已引入到SrTi（C₂O₄）₂颗粒的表面;XRD分析表明,苯胺-SrTi（C₂O₄）₂颗粒为含少量结晶的无定形态。采用SEM观察颗粒的形貌,结果表明,随反应体系中苯胺与钛原子物质的量比n_aniline/n_Ti的增大,苯胺-SrTi（C₂O₄）₂颗粒由近似球状（n_aniline/n_Ti =0）变为多面体状（n_aniline/n_Ti =2）,而后变为棒状与团簇状颗粒的混合体系（n_aniline/n_Ti =3）。以苯胺-SrTi（C₂O₄）₂颗粒为分散相制备颗粒质量分数为66.7%电流变液,电流变性能测试结果表明,在n_aniline/n_Ti =2时,电流变液具有较高的剪切应力和剪切屈服强度、较大的漏电流密度。苯胺在颗粒制备过程中起控制颗粒形貌的作用,在电流变液体系中起极性分子的作用,其对苯胺-SrTi（C₂O₄）₂电流变液性能的影响是两种效应综合作用的结果。     

ZnFe2O4纳米球的制备及其对丙酮的气敏性能研究

丙酮被广泛应用于工业和实验室,对丙酮浓度的检测十分重要。ZnFe₂O₄是一种尖晶石型三元金属氧化物,气敏性能优良,可广泛应用于气体传感器。本文采用简单的一步水热法制备了球状的ZnFe₂O₄气敏材料。通过XRD、XPS、SEM、TEM、N2吸附-解析仪对材料的形貌结构、化学组成、比表面积等进行分析,并以丙酮为目标气体对其气敏性能进行了综合研究。结果表明,ZnFe₂O₄纳米球是由纳米粒子自组装而成,有较大的比表面积;该ZnFe₂O₄基气体传感器在最佳工作温度150℃下对丙酮的灵敏度为65.74,并具有出色的选择性、稳定性、重复性,但随着湿度的增加其气敏性能逐渐降低。     

CuFe2O4/纳米纤维素磁性复合材料的制备及催化性能

采用简单易行的一锅溶剂热法原位合成CuFe₂O₄/纳米纤维素（CuFe₂O₄/CNC）磁性复合材料,并研究CuFe₂O₄/CMC磁性复合材料催化剂在NaBH₄作用下催化还原4-硝基酚（4-NP）性能。结果表明:所制备的CuFe₂O₄/CNC磁性复合材料为单一尖晶石结构,具有超顺磁性,纳米颗粒尺寸约为10 nm,其饱和磁化强度为33.15 emu·g-1。与CuFe₂O₄纳米颗粒相比,CuFe₂O₄/CNC磁性复合材料的比表面积提高到89.9 m2·g-1（CuFe₂O₄纳米颗粒的比表面积为53.9 m2·g-1）。CNC有助于改善CuFe₂O₄的单分散性,且对4-NP的吸附作用能加快反应的传质速率。将CuFe₂O₄/CNC磁性复合材料用于催化还原4-NP,反应符合一级动力学特征;当CNC的添加量为0.2 g时,可以将4-NP（100 μL,0.005 mol·L-1）溶液在25 s催化还原完全,表现出优异的反应活性。催化剂循环使用5次后,对4-NP的转化率仍能保持90%以上。      

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。     

LiMn2O4/活性炭复合材料的电化学性能研究

制备了不同比例的活性炭复合LiMn2O4电极材料,研究其在1mol/L Li2SO4溶液中的电化学性能.循环伏安结果表明复合后电极材料的电容包含活性炭的双电层电容和LiMn2O4电化学反应的法拉第电容,复合后响应电流在0～0.6V范围内有所增加,且含80%活性炭时响应电流达到最大;恒流充放电结果表明含80%活性炭时的放电曲线也基本呈直线,表现出较好的电容特性,仅复合了20%的LiMn2O4,其容量却增加了25%;交流阻抗结果表明含80%活性炭的复合电极的溶液欧姆电阻仅为0.1Ω,呈现出更理想的电容行为.