Co3O4纳米线的丙三醇辅助合成及其电化学性质

以硝酸钴和丙三醇为反应物通过反应条件的改变控制制备出Co3O4纳米线.利用粉末X射线衍射(XRD),扫描电子显微镜(SEM)和透射电子显微镜(TEM)对产物的形貌与结构进行了表征.实验发现,在低扫描速率下,Co3O4纳米线电极的循环伏安(CV)曲线呈现出两对氧化还原峰.恒电流充放电实验中,氧化钴纳米线电极在1A.g-1电流密度下的电容为163F.g-1;在1和4A.g-1条件下,其容量随循环次数的增加先上升后下降,1000次充放电循环后容量保持率分别在98%和80%以上,继续增加循环次数则容量下降比较明显.锂离子电池性质测试中,氧化钴纳米线的放电容量为1124mAh.g-1,然而放电容量随循环次数增加下降较快.基于实验结果,对Co3O4纳米线的形成机理及其结构与电化学性质之间的关系进行了探讨.     

Topochemical synthesis of cobalt oxide-based porous nanostructures for high-performance lithium-ion batteries

Two kinds of topochemical conversion routes from cobalt hydroxide precursors to cobalt oxide-based porous nanostructures are presented: pyrolysis in air and hydrothermal treatment by the Kirkendall diffusion effect. These cobalt hydroxide precursors were synthesized by a simple hydrothermal approach with sodium acetate as mineralizer at 200 °C. Detailed proof indicates that the process of cobalt hydroxide precursor growth is dominated by a nucleation, dissolution, renucleation, growth, and exfoliation mechanism. By the topochemical conversion processes several Co(3)O(4) nanostructures, such as cobalt oxide-coated cobalt hydroxide carbonate nanowires, cobalt oxide nanotubes, hollow cobalt oxide spheres, and porous cobalt oxide nanowires, have been synthesized. The obtained Co(3)O(4) nanostructures have also been evaluated as the anode materials in lithium-ion batteries. It was found that the as-prepared Co(3)O(4) nanostructures exhibited high reversible capacity and good cycle performance due to their porous structure and small size.     

Ultrathin Co3O4 nanowires with high catalytic oxidation of CO

Ultrathin Co(3)O(4) nanostructures with high catalytic oxidation of CO were synthesized by heating cobalt foils under atmospheric conditions. The Co(3)O(4) nanostructures were selectively exposing (111) planes composed of plenty of Co(3+) cations. We observed ultrahigh catalytic oxidation of CO in Co(3)O(4) nanowires with about 3 nm diameter.     

Mesoporous cobalt oxide for largely improved lithium storage properties

We report the microstructure,application for lithium-ion batteries of mesoporous Co3O4 prepared by modified KIT-6 template method.The sample was characterized by XRD,TEM,HRTEM and nitrogen adsorption.Their electrochemical behaviors as electrode reactants for lithium ion batteries were evaluated by cyclic voltammograms and static charge-discharge.A direct comparison of electrochemical behaviors between mesoporous nanostructure and bulk reflects interesting "nanostructure effect",which is reasonably discussed in terms of how the 3D nanostructures of Co3O4 materials function in tuning their electrochemistry.The results demonstrate that further improvement of electrochemical performance in transition metal-oxide-based anode materials can be realized via the design of multiporous nanostructured materials.     

泡沫镍载Co（OH）2纳米线的电化学电容性能

以无模板法制备了泡沫镍载Co(OH)2纳米线电极,利用扫描电镜(SEM)和透射电镜(TEM)观测了纳米线的表面形貌,利用X射线衍射(XRD)分析了Co(OH)2纳米线的结构,通过循环伏安、恒流充放电和交流阻抗测试了电极的电化学电容性能.结果表明:Co(OH)2呈线状生长,其直径约为300nm,长度约为8～10μm,密集地生长在泡沫镍骨架上.电流密度为10mA·cm-2时电极的放电比容量高达677F·g-1,循环500次后比容量仍保持在574F·g-1,电化学阻抗测试其电荷传递电阻仅为0.23Ω,500次循环后电荷传递电阻仅增加0.03Ω.     

Hydrothermal synthesis and structure evolution of hierarchical cobalt sulfide nanostructures

Hierarchical and well-defined cobalt sulfide with flower-like, cube-like, ball-like, and surface hollowed-out nanostructures were successfully prepared by a facile one-pot hydrothermal synthesis approach, employing Co(NO(3))(2)·6H(2)O as a cobalt precursor and thiourea as a sulfur source. The morphologies of these structures can be easily controlled by simply adjusting the molar ratio of reactants and solvents, reaction time, reaction temperature, and ligand types. Thiourea plays two important roles in the growth process of CoS nanostructures. First, it is decomposed to produce S(2-) for the final formation of CoS. On the other hand, it serves as a structure-directing agent to control the crystalline growth of CoS. The electrochemical capacitance performances of the CoS nanostructures were studied, and the flower-like CoS nanostructures show the best charge-discharge performance among all CoS products with the highest specific capacitance values of 389 F g(-1) at current density of 5 mA cm(-2), and 277 F g(-1) at higher current density of 50 mA cm(-2).     

Ternary cobalt-iron phosphide nanocrystals with controlled compositions, properties, and morphologies from nanorods and nanorice to split nanostructures

Structural phase-controlled formation of binary Co(2)P and CoP nanocrystals is achieved by reacting cobalt(II) oleate with trioctylphosphine. In the absence of oleylamine, Co(2)P nanowires are formed at both 290 and 320 °C. In the presence of oleylamine, Co(2)P nanorods are formed at 290 °C, and CoP nanorods are formed at 320 °C. With the simultaneous reaction of iron(III) oleate and cobalt(II) oleate with trioctylphosphine in the presence of oleylamine, ternary Co(2)P-type cobalt-iron phosphide nanostructures are produced at both 290 and 320 °C, corresponding to rice-shaped Co(1.5)Fe(0.5)P nanorods and split Co(1.7)Fe(0.3)P nanostructures, respectively. The controlled incorporation of iron into cobalt phosphide can alter the magnetic properties from paramagnetic binary Co(2)P to ferromagnetic Co(2)P-type ternary cobalt-iron phosphide nanostructures. Meanwhile, the time-dependent morphological evolution from small nanodots/nanorods, through seeded growth to unique split nanostructures is demonstrated in one-pot reaction at 320 °C.     

溶剂热法合成不同形貌的Co3O4及其电容特性

采用溶剂热法以不同的钴盐在水-正丁醇体系中合成了不同形貌及尺寸的纳米Co3O4. 采用XRD和TEM对产物的物相和形貌进行表征. 结果表明, 通过改变反应体系中阴离子的种类, 可以控制产物Co3O4的形貌与晶粒尺寸. 通过循环伏安法、恒流充放电和交流阻抗法对Co3O4电极材料的电化学性能进行表征. 结果表明, Co3O4的形貌与晶粒尺寸对其电化学性能有显著影响. 在2 mol·L-1 KOH溶液中, 在-0.40 - 0.55 V (vs SCE)电位范围内, 由Co(NO3)2制备的球形Co3O4表现出更好的电容特性,单电极初始比容量达362.0 F·g-1, 经过400 次循环后比容量仍保持90%.     

三维钴基MOF[KCo7(OH)3(ip)6(H2O)4]·12H2O作为超级电容器的高容量电极材料

为了开发较高能量密度的超级电容器,我们通过简单的溶剂热反应合成了一种三维的钴基金属有机框架(MOF)化合物([KCo7(OH)3(ip)6(H2O)4]·12H2O,Co?ip;ip=间苯二甲酸根),并考察了其作为超级电容器电极材料的性能。Co?ip电极显示出高比电容、良好的循环稳定性和优良的倍率性能。在1 mol·L^-1 KOH溶液中,电流密度为1 A·g^-1时,其最大比电容为1660 F·g^-1。在电流密度为2 A·g^-1条件下,循环3000次后,其比电容的保持率为82.7%。优异的超级电容性能可归因于Co?ip具有纳米尺寸颗粒和三维的多孔结构。     

Hydrothermal synthesis and pseudocapacitance properties of MnO2 nanostructures

The effect of varying the hydrothermal time to synthesize manganese oxide (MnO(2)) nanostructures was investigated along with their influence on structural, morphological, compositional, and electrochemical properties in supercapacitor electrode materials. XRD and TEM studies showed that the MnO(2) prepared in shorter hydrothermal dwell time was a mixture of amorphous and nanocrystalline particles, and there was an evolution of crystallinity of the nanostructures as the dwell time increased from 1 to 18 h. Interestingly, SEM, TEM, and HRTEM revealed a variety of structures ranging from nanostructured surface with a distinct platelike morphology to nanorods depending upon the hydrothermal reaction time employed during the preparation of the manganese oxide: increasing the amount of individual nanorods in the materials prepared with longer hydrothermal reaction time. The surface area of the synthesized nanomaterials varied from 100 to 150 m(2)/g. Electrochemical properties were evaluated using cyclic voltammetry (CV) and galvanostatic charge-discharge studies, and the capacitance values were in the range 72-168 F/g depending upon synthesis conditions. The formation mechanism of the nanorods and their impact on the specific capacitance were discussed in detail.     

Dendrite-like Co3O4 nanostructure and its applications in sensors, supercapacitors and catalysis

Dendrite-like Co(3)O(4) nanostructure, made up of many nanorods with diameters of 15-20 nm and lengths of 2-3 μm, has been successfully prepared by calcining the corresponding nanostructured Co-8-hydroxyquinoline coordination precursor in air. The Co(3)O(4) nanostructure was evaluated as an electrochemical sensor for H(2)O(2) detection and the results reveal that it has good linear dependence and high sensitivity to H(2)O(2) concentration changes. As an electrode material of a supercapacitor, it was found that the nanostructured Co(3)O(4) electrode exhibits high specific capacitance and long cycle life. The Co(3)O(4) nanostructure also has good catalytic properties and is steadily active for CO oxidation, giving 100% CO conversion at low temperatures. The multifunctional Co(3)O(4) nanostructure would be a promising functional nanomaterial applied in multi industrialized fields.     

Delamination of surfactant-intercalated brucite-like hydroxy salts of cobalt and copper and solvothermal decomposition of the resultant colloidal dispersions

Surfactant anion intercalated hydroxy salts of copper and cobalt of the formula M(OH)2- x (surf)x.mH2O [M = Cu, Co; surf = dodecyl sulfate, dodecyl benzene sulfonate, and x = 0.5 for Cu and 0.67 for Co] delaminate readily in 1-butanol to give translucent colloidal dispersions that are stable for months. The extent of delamination and the colloidal dispersion observed in these solids is higher than what had been observed for layered double hydroxides. The dispersions yield the corresponding nanoparticulate oxides on solvothermal decomposition. While the copper hydroxy salt forms approximately 300 nm dendrimer-like CuO nanostructures comprising nanorods of approximately 10 nm diameter, the cobalt analogue forms approximately 20 nm superparamagnetic particles of Co3O4.     

模板法制备的有序介孔Co3O4的电化学电容行为

以介孔硅作为模板合成有序的介孔Co3O4, 在6 mol/L KOH电解液里进行电化学性能的测试. 结果表明具有有序介孔结构的Co3O4, 其比容量可以达到250 F/g, 大约为在550 ℃下直接煅烧Co(NO3)•6H2O所得的Co3O4容量的4倍. 其外该材料还表现出良好的倍率特性, 这一现象可归因于有序的介孔结构增大了有效的反应表面积, 同时有利于离子在其中传递.     

一维有序聚苯胺纳米阵列的制备及电化学储能性能

以导电玻璃FTO为基底电极, 在硫酸溶液中, 分别研究了苯胺单体浓度和恒定电流大小对聚苯胺(PANI)形貌的影响; 同时恒定苯胺单体的浓度和工作电流, 探究了不同类型的质子酸对PANI阵列形貌的影响. 结果表明, 采用恒电流方法可以制备出一维有序PANI纳米线阵列, 而且当苯胺的浓度为0.1 mol/L, 恒电流法的工作电流密度为0.03 mA/cm²时, 所制备的PANI纳米线阵列形貌最佳; 当用HCl, HNO₃和对甲苯磺酸(p-TSA)作为合成PANI的支持液时, 得到树桩状的PANI 纳米结构, 不能得到均一的纳米线阵列结构. 电化学性能测试结果表明, 制备的最佳形貌PANI纳米线阵列的比电容值可达560 F/g; 循环1000周后电容损失率为11%.     

From layered double hydroxide to spinel nanostructures: facile synthesis and characterization of nanoplatelets and nanorods

Mg-Al spinel (MgAl2O4) nanorods and nanoplatelets transformed from Mg-Al layered double hydroxide (Mg-Al-LDHs) were synthesized via a combined hydrothermal method and calcination route using Al(NO3).9H2O and Mg(NO3)2.6H2O as raw materials. The nanorods and nanoplatelets were characterized by means of physical techniques, including powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microcopy (HRTEM), selected-area electron diffraction (SAED), Fourier transform infrared spectra (FT-IR), thermogravimetric (TG), and nitrogen adsorption-desorption isotherms. XRD patterns reveal that the Mg-Al-LDHs nanostructures were obtained under a hydrothermal reaction temperature of 200 degrees C and Mg-Al spinel nanostructures were fabricated via calcination of the Mg-Al-LDHs nanostructures at 750 degrees C. It can be seen from TEM that the sizes of the Mg-Al-LDHs nanoplatelets were about 20-40 nm and the diameters of the MgAl2O4 nanorods were ca. 6 nm. The HRTEM images indicate that the crystal lattice spaces of the MgAl2O4 nanorods and nanoplatelets are 0.282 and 0.287 nm, respectively.     

Mesoporous and nanowire Co3O4 as negative electrodes for rechargeable lithium batteries

The conversion reactions associated with mesoporous and nanowire Co(3)O(4) when used as negative electrodes in rechargeable lithium batteries have been investigated. Initially, Li is intercalated into Co(3)O(4) up to x approximately 1.5 Li in Li(x)Co(3)O(4). Thereafter, both materials form a nanocomposite of Co particles imbedded in Li(2)O, which on subsequent charge forms CoO. The capacities on cycling increase on initial cycles to values exceeding the theoretical value for Co(3)O(4) + 8 Li(+) + 8e(-) --> 4 Li(2)O + 3 Co, 890 mAhg(-1), and this is interpreted as due to charge storage in a polymer layer that forms on the high surface area of nanowire and mesoporous Co(3)O(4). After 15 cycles, the capacity decreases drastically for the nanowires due to formation of grains that are separated one from another by a thick polymer layer, leading to electrical isolation. In contrast, the mesoporous Co(3)O(4) losses its mesoporosity and forms a morphology similar to bulk Co(3)O(4) (Co particles imbedded in Li(2)O matrix) with which it exhibits a similar capacity on cycling. In contrast to mesoporous lithium intercalation compounds, which show superior capacity at high rates compared to bulk materials, mesoporosity does not seem to improve the capacity of conversion reactions on extended cycling. If, however, mesoporosity could be retained during the conversion reaction, then higher capacities could be obtained in such systems.     

A facile route to growth of γ-MnOOH nanorods and electrochemical capacitance properties

Single crystal nanorods of γ-MnOOH with lengths up to hundreds of nanometers were successfully prepared employing a novel solvothermal process based on the redox reaction between potassium permanganate (KMnO(4)) and N, N-dimethyl ammonium formate (DMF) without extra surfactant or template. The as-prepared products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Fourier transformed infrared spectroscopy (FTIR). The electrochemical properties of γ-MnOOH nanorods were investigated by cyclic voltammetry and galvanostatic charge-discharge performance measurements. Specific capacitance (C(s)) calculated from the galvanostatic discharge curve was 131.9 F g(-1) for γ-MnOOH nanorods at the current density of 0.5 A g(-1). The electrochemical experiment results demonstrate that γ-MnOOH nanorods should be a good candidate as electrode material for supercapacitor.     

静电纺氧化锰复合碳纳米纤维柔性膜的电化学性能

采用一步法静电纺丝技术制备了具有超亲水特性的氧化锰/碳纳米纤维(MnO_x/CNFs)复合柔性膜电极材料,并通过X射线衍射、扫描电子显微镜和透射电子显微镜等对复合材料进行了表征.电化学性能测试结果表明,复合材料的电容性能优于单一材料,醋酸锰质量分数为40%时制得的复合纳米纤维电极(MC-4)在1 A/g电流密度下,于2 mol/L KOH电解液中的比电容高达1112.5 F/g,10 A/g电流密度下循环3000次比容量保持在93.4%,具有很好的稳定性.MnO_x/CNFs复合材料电化学性能增强一方面是由于三维超亲水纤维膜结构有利于电解液的快速浸润渗透,从而极大缩短了传输到材料基质的有效路径;另一方面是由于碳和MnO_x的协同效应,包裹在MnO_x粒子周围的碳层避免了MnO_x在充放电过程中的体积膨胀效应,这2种叠加机制促进了电化学性能的提升.     

孔状Co_3O_4纳米片和纳米棒的选择性合成和表征(英文)

利用两步实验选择性合成孔状Co3O4纳米片和纳米棒:首先,以Co(NO3)2·6H2O,NaOH和不同量的NH4F为原料在120℃水热6h的条件下合成了Co(OH)2-Co3O4纳米片(S1)和Co(OH)F-Co3O4纳米棒(S2);然后将所得纳米片和纳米棒在400℃时加热2h即得到多孔的Co3O4纳米片和纳米棒。所得产物用X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)和透射电子显微镜(TEM)进行了表征。此外电化学测试表明Co3O4纳米棒的电容量比Co3O4纳米片的更大。     

MnO@Carbon Core–Shell Nanowires as Stable High‐Performance Anodes for Lithium‐Ion Batteries

A facile method is presented for the large‐scale preparation of rationally designed mesocrystalline MnO@carbon core–shell nanowires with a jointed appearance. The nanostructures have a unique arrangement of internally encapsulated highly oriented and interconnected MnO nanorods and graphitized carbon layers forming an external coating. Based on a comparison and analysis of the crystal structures of MnOOH, Mn₂O₃, and MnO@C, we propose a sequential topotactic transformation of the corresponding precursors to the products. Very interestingly, the individual mesoporous single‐crystalline MnO nanorods are strongly interconnected and maintain the same crystallographic orientation, which is a typical feature of mesocrystals. When tested for their applicability to Li‐ion batteries (LIB), the MnO@carbon core–shell nanowires showed excellent capacity retention, superior cycling performance, and high rate capability. Specifically, the MnO@carbon core–shell nanostructures could deliver reversible capacities as high as 801 mA h g^?1 at a high current density of 500 mA g^?1, with excellent electrochemical stability after testing over 200 cycles, indicating their potential application in LIBs. The remarkable electrochemical performance can mainly be attributed to the highly uniform carbon layer around the MnO nanowires, which is not only effective in buffering the structural strain and volume variations of anodes during repeated electrochemical reactions, but also greatly enhances the conductivity of the electrode material. Our results confirm the feasibility of using these rationally designed composite materials for practical applications. The present strategy is simple but very effective, and appears to be sufficiently versatile to be extended to other high‐capacity electrode materials with large volume variations and low electrical conductivities.