Fe-based phosphate nanostructures for supercapacitors

Fe-based phosphates with excellent physical and chemical features are potential electrode materials for supercapacitors.In this work,we successfully synthesized Fe-based phosphates with different dimensions,morphologies,and compositions by one-step hydrothermal method.Influence factors on the chemical composition and morphology of the as-prepared materials were explored and the energy storage performance of the as-prepared samples were tested under the traditional three electrode system.Two-dimensional(2 D) iron metaphosphate(Fe(PO_3)_3) showed the best electrochemical performance.For Fe(PO_3)_3 electrode mate rials,the layered structure can provide a larger specific surface area than the bulk structure,which is conducive to the diffusion and transport of electrolyte ions during charging-discha rging and further improve s the rate perfo rmance and cycle stability of supe rcapacito r.2 D Fe(PO_3)_3 and activated carbon were used as electrode materials to construct a 2 D Fe(PO_3)_3//AC supercapacitor.The supercapacitor showed high energy density,high power density,and excellent cycling stability,which indicates 2 D Fe(PO_3)_3 is a promising electrode material for supercapacitors.     

基于碳材料的超级电容器电极材料的研究

超级电容器作为一种新型的能源存储装置,因为其比容量大、充放电速度快、循环寿命长等优点,在储能领域引起了极为广泛的关注。电极材料是决定超级电容器性能的核心因素,其中,常用的超级电容器电极材料主要有如下三类:碳基材料、金属氧化物及氢氧化物材料和导电聚合物材料。本文综述了超级电容器的工作原理并详细介绍了基于碳材料及其二元、三元复合体系的电极材料的研究进展。     

Investigating metal-organic framework as a new pseudo-capacitive material for supercapacitors

A new application of metal organic framework （MOF） as a pseudo-capacitive material for supercapacitors is investigated. To this end, a simple nickel-based MOF, formulated Ni3（btc）2.12H2O, is synthesized via a hydrothermal reaction. As an electro-active material, such nickel-based MOF exhibits superior pseudo- capacitive behavior in KOH aqueous electrolyte with a high specific capacitance of 726 F g-1. Also, it displays good electrochemical stability with 94.6% of the initial capacitance over consecutive 1000 cycles. In addition, a simple asymmetric supercapacitor with a high energy density of 16.5 Wh kg-1 is successfully built using the nickel-based MOF as positive electrode and commercial activated carbon as negative electrode in KOH electrolyte.     

A new,improved sensor for ascorbate determination at copper hexacyanoferrate modified carbon film electrodes

A new, improved sensor for the electrocatalytic determination of ascorbate has been developed that has both a low applied operating potential and a low detection limit. The sensor was constructed by depositing copper hexacyanoferrate film either electrochemically or chemically onto carbon film electrode, and it was then characterised by cyclic voltammetry and electrochemical impedance spectroscopy. Chemically deposited films were shown to be the best for ascorbate determination and were used as an amperometric sensor at +0.05 V versus SCE to determine ascorbate in wines and juice. The linear range extended to 5 mM with a limit of detection of 2.1 M, the sensor was stable for more than four months, and it could be used continuously for at least 20 days.     

Metals in biology: Electronic structure,properties and charge transfer for copper complexes of glyoxal and dithiene

Summary In an attempt to study the role of metals in biologyab initio SCF calculations have been performed on a model complex simulating the binding between metals and biological materials. There is a certain distinction between the copper complexes compared to the other transition metals and in many cases the copper complexes are more similar to the Li and Be complexes than to other transition metal complexes. One special feature of the copper complexes is their strong ability for an easy transfer between the Cu(I) and Cu(II) states, allowing for a very flexible charge transfer with small energies required for the redox processes. These processes have been described in terms of orbital energies and Mulliken populations.Dedicated to Professor Inga Fischer-Hjalmars on the occasion of her 75th birthday     

Nafion基氧化还原聚合物在空气中的电荷传输性能

利用三明治电池和伏安法测试了不同制备条件的Nafion基氧化还原聚合物膜在空气中的电荷传输性能. 研究结果表明, 混合适量聚乙二醇(PEG)的Nafion基金属联吡啶配合物{Nafion[M(bpy)2+3, PEG](M=Ru, Fe)}膜的表观电荷传递扩散系数(Dct)达到10-6-10-7 cm2·s-1 , 电子或空穴迁移率(μ)达到10-4-10-5 cm2·V-1·s-1. 在导电玻璃(ITO)电极与Nafion基氧化还原聚合物膜界面引入一层导电聚苯胺(PANI)后, 降低了其接触电阻, 使氧化还原聚合物膜的Dct提高至10-5-10-6 cm2·s-1, μ提高至10-3-10-4 cm2·V-1·s-1, 且工作电流提高了近两个数量级. 该固态氧化还原聚合物膜的性能比较稳定, 在空气中放置30天后其Dct和μ降低得很少.     

Characterization of cobalt- and copper hexacyanoferrate-modified carbon film electrodes for redox-mediated biosensors

Cobalt and copper hexacyanoferrate films (CoHCF and CuHCF) were formed at carbon film electrodes by three different one-step processes: cycling the applied potential, application of a constant current, and chemically. All hexacyanoferrate films obtained were characterized electrochemically by cyclic voltammetry and electrochemical impedance spectroscopy. To evaluate their possible use as redox mediators for biosensors, they were applied to the determination of hydrogen peroxide in neutral phosphate buffer saline electrolyte. Chemically deposited CuHCF was found to be generally the most suitable as a mediator, although CoHCF made by potential cycling is the most useful when a very low detection limit is necessary.Dedicated to Professor George Horanyi on the occasion of his 70th birthday, in recognition of his outstanding contributions to electrochemistry.     

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l⁻¹ acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96×10⁻⁴ to 1.07×10⁻³ mol l⁻¹ with a detection limit of 8.0×10⁻⁵ mol l⁻¹. The relative standard deviation was 1.2% for 1.96×10⁻⁴ mol l⁻¹ isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method.     

Electrochemical performance of NaCo2O4 as electrode for supercapacitors

Sub-micron-scaled sodium cobalt oxide （NaCo2O4） powders are prepared by a solid-state reaction method. Characterization using X-ray diffraction indicates that the synthesized NaCo2O4 has a hexagonal layered structure. The electrochemical performance of the NaCo2O4 electrodes is investigated using cyclic voltarnmetry and galvanostatic charge/discharge in NaOH solution. The results show that the specific capacitance of the NaCo2O4 electrode reaches 337 F/g over the potential range of 0.15-0.65 V at a mass normalized current of 50 mA/g. Moreover, NaCo2O4 exhibits very good stability and cycling performance as a supercapacitor material.     

Facile Self-templating Melting Route Preparation of Biomass-derived Hierarchical Porous Carbon for Advanced Supercapacitors

Biomass-derived porous carbons show great potential as electrode materials for supercapacitors due to the environmental friendliness. However, most of the carbonaceous electrode materials suffer from low specific capaci-tance and rate capacity because of the poor porosity. Here, we reported a simple and effective approach to prepare micro/nano-hierarchical structured carbon materials derived from rice husk by NaOH-KOH molten salt co-activation. The as-prepared activated carbons exhibit high porosity and suitable pore size distributions for more electrolyte ion adsorption, which are all beneficial for achieving remarkable electrochemical performances, such as high specific capacitance(194.6 F/g), excellent rate capability(retention of 85.9%) and outstanding cycling stability. Thus, the above biomass-derived carbon materials with high porosity and micro/nano structures obtained by co-activation method offered a new insight into novel electrode material for the use in energy storage systems with high energy density and excellent rate performance.     

聚吡咯/海藻酸钠纳米球的制备及其应用于高性能超级电容器

用海藻酸钠作为结构导向剂,通过原位氧化聚合吡咯法制备了聚吡咯/海藻酸钠(PPy/SA)纳米球.聚吡咯/海藻酸钠纳米球的形貌和结构通过扫描电镜(SEM)、X射线衍射(XRD)和傅里叶变换红外(FTIR)光谱进行表征.材料的电化学性能通过循环伏安法和恒电流充放电方法进行测试.电化学测试表明,聚吡咯/海藻酸钠纳米球在1 mol L-1KCl电解液中,电流密度为1 A g-1时其比电容高达347 F g-1.与纯聚吡咯相比较,聚吡咯/海藻酸钠纳米球具有更优异的循环稳定性能.     

改性硅藻土负载亚铁氰化铜复合物的制备及其对Cs+的吸附性能

采用水热法、以氯化铝为铝源对硅藻土(De)进行改性,通过浸渍法将亚铁氰化铜(KCuHCF)纳米颗粒负载于改性De表面,制备出γ-AlOOH/De-KCuHCF和γ-Al₂O₃/De-KCuHCF两种复合吸附剂,对所制备的吸附剂进行了表征,并研究了其对Cs⁺的吸附性能。结果表明,所制备吸附剂具有优异的Cs⁺吸附性能,γ-AlOOH/De-KCuHCF和γ-Al₂O₃/De-KCuHCF最高吸附容量分别可达75.44、84.02 mg·g^-1,γ-Al₂O₃/De-KCuHCF对模拟卤水中Cs⁺的吸附率高达97.55%;以3 mol·L^-1 NH₄NO₃为脱附剂,经3级连续脱附后,γ-Al₂O₃/De-KCuHCF的Cs⁺脱附率可达81.88%,经过5次吸附-脱附循环后仍保持了较高的吸附量。     

植物基多孔炭材料在超级电容器中的应用

植物基多孔炭具有发达的孔结构、大的表面积、较为成熟的制备工艺、丰富的来源、低廉的价格,是目前商业应用范围最广的超级电容器电极材料。然而在实际应用中仍然存在着质量/体积比容量较低、倍率性能差等问题。本文针对先进电容器件的高能量密度、优异功率性能的要求,首先介绍了近年来发展的植物基多孔炭的制备方法,讨论了植物前驱体的组成和结构对其产物结构的影响以及与其电化学性能之间的构效关系,特别总结了近年来植物基超大比表面积多孔炭、中孔炭、层次化多孔炭的制备方法和电容储能性能。针对大比表面积多孔炭用于超级电容器时的体积性能不佳这一关键问题,本文还总结了提高植物基多孔炭体积电化学性能的方法。最后,对植物基多孔电极材料存在的问题进行了分析与总结,并展望了其研究前景。     

Voltammetric determination of N-acetylcysteine using a carbon paste electrode modified with copper(II) hexacyanoferrate(III)

The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s^− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10^− 4 to 8.3 × 10^− 4 mol L^− 1, with a detection limit of 6.3 × 10^− 5 mol L^− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.     

Design and Preparation of Graphene/Fe2O3 Nanocomposite as Negative Material for Supercapacitor

The development of high specific capacitance electrode materials with high efficiency, scalability and economic feasibility is significant for the application of supercapacitors, however, the synthesis of electrode material still faces huge challenges. Herein, graphene(G)/Fe₂O₃ nanocomposite was prepared via a simple hydrothermal method connected with subsequent thermal reduction process. Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) results showed rod-like Fe₂O₃ nanoparticles were prepared and well-dispersed on graphene layers, providing a rich active site and effectively buffering the aggregation of Fe₂O₃ nanoparticles in the process of electrochemical reaction. The specific capacitance of the obtained G/Fe₂O₃ nanocomposite as negative electrode for supercapacitor was 378.7 F/g at the current density of 1.5 A/g, and the specific capacitance retention was 88.76% after 3000 cycles. Furthermore, the asymmetric supercapacitor(ASC) was fabricated with G/Fe₂O₃ nanocomposite as negative electrode, graphene as positive electrode, which achieved a high energy density of 64.09 W∙h/kg at a power density of 800.01 W/kg, maintained 30.07 W∙h/kg at a power density of 8004.89 W/kg, and retained its initial capacitance by 78.04% after 3000 cycles. The excellent result offered a promising way for the G/Fe₂O₃ nanocomposite to be applied in high energy density storage systems.     

In-situ oxidation of block copolymer for producing copper oxalate or copper oxide nanowires in mesoporous channels

Copper oxalate nanowires inside the channels of mesoporous SBA-15 are created by in-situ oxidation of block copolymer in as-prepared SBA-15 samples. The pyrolysis of CuC₂O₄/SBA-15 composites under different conditions results in the formation of CuO or Cu₂O nanowires encapsulated in the nanoscale channels. The appearance, structure and composition of these materials are characterized by the X-ray power diffraction, transmission electron microscopy, N₂ adsorption-desorption isotherms, infrared spectra and inductive coupled plasma emission spectra. CuC₂O₄, CuO and Cu₂O nanomaterials filled in the channels of SBA-15 have been proven to possess the electrochemical hydrogen storage capacities of 102, 165 and 231 mAh/g in the second cycle, respectively, and are expected to have a high potential for use in practical applications.     

改性硅藻土负载亚铁氰化铜复合物的制备及其对Cs+的吸附性能

采用水热法、以氯化铝为铝源对硅藻土(De)进行改性,通过浸渍法将亚铁氰化铜(KCu HCF)纳米颗粒负载于改性De表面,制备出γ-Al OOH/De-KCu HCF和γ-Al₂O₃/De-KCu HCF两种复合吸附剂,对所制备的吸附剂进行了表征,并研究了其对Cs⁺的吸附性能。结果表明,所制备吸附剂具有优异的Cs⁺吸附性能,γ-Al OOH/De-KCu HCF和γ-Al₂O₃/De-KCu HCF最高吸附容量分别可达75.44、84.02 mg·g^-1,γ-Al₂O₃/De-KCu HCF对模拟卤水中Cs⁺的吸附率高达97.55%;以3 mol·L^-1NH₄NO₃为脱附剂,经3级连续脱附后,γ-Al₂O₃/De-KCu HCF的Cs⁺脱附率...     

In situ X-ray absorption spectroscopic investigation of the electrochemical conversion reactions of CuF2-MoO3 nanocomposite

We have used X-ray absorption spectroscopy at the Cu K-edge to investigate the electrochemical conversion reaction of 20 nm size 85 wt% CuF₂−15 wt% MoO₃ nanocomposite under in situ conditions. The nanocomposite was prepared by high energy milling. Upon discharge, the lithiation reaction with the nanocomposite resulted in the formation of nanophase metallic Cu, which is consistent with the conversion of CuF₂ into Cu and LiF. Based on XANES and Fourier transforms of EXAFS spectra, we show that the discharge process proceeded via the formation of highly dispersed Cu particles. Based on the coordination number of the first shell of Cu, the average size of the Cu particles was estimated to be in the 1-3 nm range in the fully discharged state.     

高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

Enhanced electrochemical performance and mechanism study of AgLi1/3Sn2/3O2 for lithium storage

Herein, AgLi_1/3Sn_2/3O₂ with delafossite structure was prepared by treating the layered compound Li₂SnO₃ with molten AgNO₃ via ion exchange of Li⁺ for Ag⁺. The structure characterization and the electrochemical performance of AgLi_1/3Sn_2/3O₂ was thoroughly investigated. AgLi_1/3Sn_2/3O₂ is found to possess stacking lamellar morphology, which means small electrochemical impedance and so facilitates charge transfer kinetics during the cycling. Compared with Li₂SnO₃, due to the introducing of excellent electrical conductivity of silver, AgLi_1/3Sn_2/3O₂ exhibits improved electrochemical performance in terms of capacity, cycling stability and coulombic efficiency. The results show AgLi_1/3Sn_2/3O₂ presents favorable specific capacity of 339 mAh/g at current density of 200 mA/g after 50 cycles and initial coulombic efficiency of 96%. Ex situ XRD analysis revealed the reaction mechanism of AgLi_1/3Sn_2/3O₂ as an anode for lithium ion batteries.