Enhancing the performances of Li-ion batteries by carbon-coating: present and future

With progress of knowledge of electrode materials, it has been found that their surface structures are of great importance to the electrochemical performance of Li-ion batteries. Carbon coating can effectively increase the electrode conductivity, improve the surface chemistry of the active material, and protect the electrode from direct contact with electrolyte, leading to enhanced cycle life of the batteries. Carbon coating together with nanotechnology provides good conductivity as well as fast Li-ion diffusion, and thus also results in good rate capabilities. The recent development of carbon coating techniques in lithium-ion batteries is discussed with detailed examples of typical cathode and anode materials. The limitation of current technology and future perspective of the new concept of "hybrid coating" are also pointed out.     

锰酸镧和氧化钇稳定的氧化锆复合阴极的研究

用交流阻抗,强极化和电导测量等方法考察了一系列不同氧化钇稳定氧化锆(YSZ)含量的锶掺杂锰酸镧(LSM)复合阴极的电化学性能,发现随着掺入YSZ量的增大,阴极性能大幅度提高,当YSZ质量分数为40%时,电极性能最好,电化学极化电阻约为1.18Ω/cm².通过分析发现,YSZ的掺杂使电极反应过程的控制步骤发生了变化.同时发现,随着YSZ含量的增加,电极的接触电阻增大.以Pt为电流收集层和40%的YSZ+LSM的复合电极形成的二层电极可有效地消除接触电阻,进一步提高了复合电极的性能.在1223K极化电阻从1.18Ω/cm²下降到0.41Ω/cm².     

FeOOH@Fe3O4复合材料合成及超级电容特性研究

以FeOOH为基质,氯化铁为铁源,通过溶剂热法制备得到包覆四氧化三铁的氧化铁黄。分别采用粉末X射线衍射(XRD)、扫描电镜(SEM)和热重-差热分析(TG-DTA)等技术对包覆层物质及复合产物的结构和性质进行表征。结果表明:通过溶剂热法合成的复合产物表层是四氧化三铁结构,内部为羟基氧化铁。电化学测试结果表明FeOOH@Fe3O4在0.1A·g-1电流密度下比容量为89F·g^-1,在该电流密度下循环800次,容量维持在80%左右,优于FeOOH和Fe3O4;FeOOH@Fe3O4复合产物的比表面积为17.08m^2·g^-1,且FeOOH@Fe3O4电极内阻为1.45Ω,低于FeOOH和Fe3O4,这主要是由于FeOOH@Fe3O4有效结合了FeOOH比表面积大和四氧化三铁导电性高的优势,扩大了电解液离子与电极活性物质的接触面积,提高了电子和离子在电极材料中的传递速率。     

Inverse opal carbons for counter electrode of dye-sensitized solar cells

We investigated the fabrication of inverse opal carbon counter electrodes using a colloidal templating method for DSSCs. Specifically, bare inverse opal carbon, mesopore-incoporated inverse opal carbon, and graphitized inverse opal carbon were synthesized and stably dispersed in ethanol solution for spray coating on a FTO substrate. The thickness of the electrode was controlled by the number of coatings, and the average relative thickness was evaluated by measuring the transmittance spectrum. The effect of the counter electrode thickness on the photovoltaic performance of the DSSCs was investigated and analyzed by interfacial charge transfer resistance (R(CT)) under EIS measurement. The effect of the surface area and conductivity of the inverse opal was also investigated by considering the increase in surface area due to the mesopore in the inverse opal carbon and conductivity by graphitization of the carbon matrix. The results showed that the FF and thereby the efficiency of DSSCs were increased as the electrode thickness increased. Consequently, the larger FF and thereby the greater efficiency of the DSSCs were achieved for mIOC and gIOC compared to IOC, which was attributed to the lower R(CT). Finally, compared to a conventional Pt counter electrode, the inverse opal-based carbon showed a comparable efficiency upon application to DSSCs.     

Wall-jet conductivity detector for microchip capillary electrophoresis

A new end-column ‘hybrid’ contactless conductivity detector for microchip capillary electrophoresis (CE) was developed. It is based on a “hybrid” arrangement where the receiving electrode is insulated by a thin layer of insulator and placed in the bulk solution of the detection reservoir of the chip, whereas the emitting electrode is in contact with the solution eluted from the channel outlet in a wall-jet arrangement. The favorable features of the new detector including the high sensitivity and low noise, can be attributed to both the direct contact of the ‘emitting’ electrode with the analyte solution as well as to the insulation of the detection electrode from the high DC currents in the electrophoretic circuit. Such arrangement provides a 10-fold sensitivity enhancement compared to currently used on-column contactless conductivity CE microchip detector as well as low values of noise and easy operation. The new design of the wall-jet conductivity detector was tested for separation of explosive-related methylammonium, ammonium, and sodium cations. The new detector design reconsiders the wall-jet arrangement for microchip conductivity detection in scope of improved peak symmetry, simplified study of inter-electrode distance, isolation of the electrodes, position of the wall-jet electrode to the separation channel, baseline stability and low limits of detection.     

介电力显微镜探测氧化锌纳米线表面吸附分子对电导率的影响

利用场效应晶体管器件和介电力显微镜来研究氧化锌纳米线表面吸附分子对其电导率的影响. 相比于空气中,ZnO纳米线场效应晶体管器件在氮气中电导率更高,介电力显微镜得的介电信号也是在氮气中更大. 影响ZnO纳米线电导率变化的主要原因是表面吸附分子数量的变化,而并不是电极与材料之间接触性质的变化.     

A self-cleaning nonenzymatic glucose detection system based on titania nanotube arrays modified with platinum nanoparticles

In the present work, we show how TiO₂ nanotube layers that are decorated with a Pt-nanoparticle coating can be fabricated and operated as a reusable glucose sensing system. A critical amount of Pt coating is essential not only to provide an effective catalyst for glucose oxidation but also to establish a sufficient conductivity along TiO₂ nanotube walls to allow an efficient amperometric operation of the electrode. On such an electrode the self-cleaning photocatalytic features of TiO₂ can be maintained and used to re-establish poisoned activity of the Pt particles.     

Electrochemical characteristics and interfacial contact resistance of Ni-P/TiN/PTFE coatings on Ti bipolar plates

The Ni-P/TiN/PTFE (poly tetra fluoroethylene) composite coatings were prepared by electroless plating method on Ti plate, which was used as bipolar plates of proton exchange membrane fuel cells (PEMFCs). The morphology, crystallographic texture, electrochemical corrosion, contact resistance, and hydrophobic property of the Ti bipolar plates with coatings were investigated. The results revealed that Ni-P/TiN/PTFE coating had a dense surface morphology, uniform distribution of composite particles. Ti with coating showed 0.48 μA cm² of corrosion current in the simulated solution of PEMFCs and 6 mΩ cm² of interfacial contact resistance (ICR). The hydrophobicity test showed that the coating interface was flat and the wetting angle was 112.4°. In conclusion, The Ni-P/TiN/PTFE composite coatings exhibit superior improvement in corrosion resistance, interface hydrophobicity, and conductivity to Ni-P, Ni-P/TiN, and Ni-P/PTFE coatings. The Ni-P/TiN/PTFE coating was suited for bipolar plate surface modification of bipolar plates.     

等离子体增强化学气相沉积法制备WO3-x/C复合材料及其储锂性能研究

三氧化钨(WO_3)凭借其在锂离子电池中较高的理论比容量(～700mAh·g~(-1))以及廉价易得的特性而引起了科研工作者广泛的研究兴趣,然而其相对较差的导电性以及在循环过程中所发生的较大体积变化导致其倍率性能和循环性能并不理想。为了增强其导电性,减缓体积变化所带来的负面影响,本文采用等离子体增强的化学气相沉积法成功地在所制备的WO_(3-x)纳米片上包覆含有氮元素掺杂的无定形碳。氮掺杂碳的包覆可以有效降低循环过程中发生的较大体积变化问题,而且可以提供更多的位点供锂离子进行嵌入/脱嵌。电化学测试表明,所制备的WO_(3-x)/C电极相比于WO_(3-x)电极和商业WO_3电极,展现出更好的倍率性能和循环性能。动力学模拟与计算表明,经过碳包覆的WO_(3-x)/C电极具有更小的电荷转移电阻和更快的锂离子扩散速率,从而有效提升其电化学性能。     

Electrochemical and XPS study of LiFePO4 cathode nanocomposite with PPy/PEG conductive network

High performance PPy/PEG-LiFePO₄ nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO₄ particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO₄ composites are more effective than bare LiFePO₄ as cathode material.     

透明抗静电多功能超疏水薄膜的制备

采用提拉法在聚酰亚胺薄膜表面分步涂覆了银纳米线及疏水纳米二氧化硅, 分别构筑了导电网络及超疏水涂层, 制备了超疏水抗静电透明薄膜. 研究结果表明, 超疏水抗静电透明薄膜保持了较高的透光性, 其透光率高于90%. 同时, 银纳米线网络的构筑有效增加了超疏水抗静电透明薄膜的导电性, 使其表面电阻介于10⁶~10¹⁰ Ω之间, 达到了抗静电要求. 水滴在该薄膜表面静态接触角高达156.4°, 滚动角小于1°, 展现了优异的超疏水特性. 通过导电网络及疏水涂层的构筑, 实现了透明及抗静电超疏水多功能的统一.     

镧掺杂的二氧化锰/碳纳米管电化学超级电容器复合电极

尽管在二氧化锰/多壁碳纳米管（MnO₂/MWCNTs）上获得了较高的比电容,低电导率仍是制约MnO₂担载量或膜厚度提高的主要障碍.另一个问题是MnO₂/MWCNTs的循环稳定性远低于活性炭.所以截止到目前这一新型材料的应用仍然受到很大的限制.本文采用原位还原的方法制备镧掺杂二氧化锰/多壁碳纳米管电化学超级电容器复合电极材料.分别通过透射电镜（TEM）、扫描电镜（SEM）、X射线衍射（XRD）和傅里叶变换红外（FTIR）光谱等技术对这些复合材料的形貌与结构进行了分析.采用循环伏安法、恒电流充放电法和交流阻抗法对其进行了电化学性能的研究.研究结果表明,通过还原MnO₄^-可以在MWCNTs上形成La掺杂MnO₂复合材料.La掺杂降低了复合电极的电阻,这是因为La的引入可以增大MnO₂的晶格缺陷,从而提高材料的电导率以及电极的电化学性能.因此La掺杂是克服MnO₂本征导电性差的有效途径之一.掺杂La可以在不增大电极电阻的情况下提高MnO₂的担载量或膜厚度.La掺杂的更重要的作用是使以MnO₂/MWCNTs作电极的对称电化学超级电容器的循环性能得到显著改善.此外,La掺杂也使复合电极的比电容得到一定程度的提高.     

用于超级电容器的锰钴氧化物/碳纤维材料

The development of high-performance supercapacitor electrode materials is imperative to alleviate the ongoing energy crisis. Numerous transition metals (oxides) have been studied as electrode materials for supercapacitors owing to their low cost, environmental-friendliness, and excellent electrochemical performance. Among the developed binary transition metal oxides, manganese cobalt oxides typically show high theoretical capacitance and stable electrochemical performance, and are widely used in the electrode materials of supercapacitors. However, the poor conductivity and active material utilization of manganese cobalt oxide-based electrode materials limit their potential capacitance application. Cotton is mainly composed of organic carbon-containing materials, which can be transformed to carbon fibers after calcination. The resultant carbonaceous material exhibits a large specific surface area and good conductivity. Such advantages could potentially suppress the negative effects caused by the poor conductivity and small specific surface area of manganese cobalt oxides, thereby improving the electrochemical performance. Herein, we firstly deposited manganese cobalt oxides on cotton by a simple hydrothermal method, yielding a composite of manganese cobalt oxides and carbon fibers via subsequent calcination, to improve the electrochemical performance of the electrode material. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), and electrochemical characterizations were used to investigate the physical, chemical, and electrochemical properties of the prepared samples. The fabricated manganese cobalt oxides in the composite were uniformly dispersed on the carbon fiber surface, which increased the contact between the interface of the electrode material and electrolyte, and enhanced electrode material utilization. The electrode material was confirmed to have well contacted with the electrolyte during a contact angle test. Hence, a pseudo-capacitance reaction completely occurred on the manganese cobalt oxide material. Moreover, the addition of carbon fibers reduced the resistance of the material, resulting in excellent capacitive performance. The capacitance of the prepared composite was 854 F∙g^-1 at a current density of 2 A∙g^-1. The capacitance was maintained at 72.3% after 2000 cycles at a current density of 2 A∙g^-1. These results indicate that the manganese cobalt oxide and carbon fiber composite is a promising electrode material for high-performance supercapacitors. The findings presented herein provide a strategy for coupling with carbon materials to enhance the performance of supercapacitor electrode materials based on manganese cobalt oxides. Thus, novel insights into the design of high-performance supercapacitors for energy management are provided.     

絮状三元镍钴铁氢氧化物电极材料的制备及其电化学储能性能

采用一步溶剂热法在泡沫镍(NF)基底上合成了镍钴氢氧化物、镍铁氢氧化物及镍钴铁氢氧化物3种电极材料,并对其电化学性能进行测试,结果表明:三元镍钴铁金属电极的储能性能要远大于其他2种二元金属电极,其在2 mA·cm-2电流密度下能达到5.11 F·cm-2的面积比电容,并且构筑的非对称超级电容器在功率密度为46.814 ...     

导电高分子在神经界面电极中的应用

神经界面电极作为人体和外部器件间信息融合的媒介, 为人们进一步探究神经系统高级功能的机制提供了有效工具. 传统的神经电极多以金属和半导体材料为主, 这两类材料因具有惰性材料的特性及优越的 导电性能而成为早期神经电极的主要制备材料, 但由于其刚性过大和光滑表面导致的机械失配及与生物组织间过高的电化学阻抗限制了神经电极的进一步发展. 导电高分子作为一种有机导电材料, 同时具备柔软性 (杨氏模量约在0.01~10 GPa)和导电性(高掺杂度的导电高分子的电导率在金属范围, 10⁰~10⁵ S/cm)的特征, 是制备神经电极的有效材料. 近年来, 人们利用导电高分子材料对传统电极材料进行改性甚至替代, 以提高电极比表面积、 减小界面阻抗, 并提高电极检测的灵敏性; 同时减小电极与组织间的应变失配, 减少炎症反应, 并进一步在导电高分子中引入功能性生物大分子, 减少生物组织对电极的排异反应, 增加电极在体内长期植入的稳定性. 本文讨论和总结了导电高分子材料在神经电极中的应用, 分别对导电高分子作为涂层修饰神经电极、 全导电高分子材料神经电极及导电高分子复合材料神经电极等展开讨论, 分析了导电高分子在神经界面电极中的应用前景及存在的问题, 以期对神经界面电极在脑科学和生物电子医疗等前沿领域的进一步发展提供参考.     

Kinetic analysis of the hydrogen oxidation reaction on Pt-black/Nafion electrode

The hydrogen oxidation reaction on Pt-black/Nafion electrode was investigated using a rotating disk electrode and cyclic voltammetry technique. The voltammetric results demonstrated that the electrode can be prepared with good reproducibility and that Pt-black particles without direct contact with Nafion were still electrochemically active in taking part in the H-adsorption/desorption process. For hydrogen oxidation, the limiting current density was reduced by the presence of Nafion coating. The H₂ diffusion resistance in Nafion film was avoided when the film thickness was less than 0.2 μm for a Pt-black loading of 20 μg. Moreover, the uncertainties in the kinetic results were discussed.     

A method for studying swelling kinetics based on measurement of electrical conductivity

A novel method was applied to the study of swelling kinetics of pH-responsive hydrogels. This technique is based on the pH-dependent electrical conductivity of these materials, which is measured by coating planar interdigitated electrode arrays with thin hydrogel membranes. To demonstrate the utility of the method, the swelling kinetics of a well-characterized pH-responsive hydrogel were studied. Cross–linked copolymers of 2-hydroxyethyl methacrylate (HEMA) with up to 20 mol% dimethylaminoethyl methacrylate (DMA) were studied as a function of copolymer composition in phosphate or triethanolamine buffer at buffer concentrations from 1 to 100 mM. The experiments consisted of measuring the change in electrical resistance of a hydrogel-coated electrode array following a small pH change in the external buffer medium. The characteristic response time to reach a new equilibrium following a pH change was proportional to the concentration of DMA within the polymer and was inversely proportional to the buffer concentration. The characteristic response times for devices tested in phosphate buffer were a function of the magnitude of the pH step, increasing from 2.6 to 5.6 min as the step size increased from 0.2 to 0.57 pH units. However, the response times for devices tested in triethanolamine were independent of step size. The observed dependences upon the values of the dissociation constant (pK_a) of the buffering ion, the apparent pK_a of DMA, and the pH of the external bath agreed with buffer-mediated diffusion–reaction theory, and as such this conductimetric method represents a powerful tool for the study of swelling kinetics of responsive hydrogels.     

Transport in ceria electrolytes modified with sintering aids: effects on oxygen reduction kinetics

Small (2 mol%) cobalt oxide additions to ceria-gadolinia (CGO) materials considerably improve sinterability, making it possible to obtain ceramics with 95–99% density and sub-micrometre grain sizes at 1,170–1,370 K. The addition of Co causes a significant shift of the electrolytic domain to lower pO₂. This modification to the minor electronic conductivity of the electrolyte material has influence on the cathodic oxygen reduction reaction. The impedance technique is shown to provide information not only about polarisation resistance, but also about the active electrode area from analysis of the current constriction resistance. It is demonstrated that this current constriction resistance can be related to the minor electronic contributions to total conductivity in these materials. A simple imbedded grid approach gives control of the contact area allowing the properties of the electrolyte materials to be studied. A much lower polarisation resistance for the Co-containing CGO electrolyte is observed, which can be clearly attributed to an increased three-phase reaction area in the Co-containing material, as a consequence of elevated p-type conductivity.     

氧化石墨烯/超细银粒子复合物的制备及其光电性能

超细银粉在太阳能电池正面电极领域有广阔的应用前景,其粒径分布、分散性、表面态与其性能息息相关。 本文通过在液相还原法合成超细银粉的后期引入氧化石墨烯(GO),利用溶液状态下二者相对活性的表面的相互作用获得了性能优良的银粉。 通过X射线衍射(XRD)、拉曼光谱(Raman)和扫描电子显微镜(SEM)等手段对所得复合超细银粉进行结构及形貌表征,结果显示该法获得的银粉分散性较好、尺寸分布较窄。 进而,利用紫外-可见光谱探讨了GO与银粒子之间的相互作用。 而且研究发现:固定硝酸银溶液的浓度,随着GO含量的增加,银粉的导电性能先升高后降低,当GO的质量分数为2.5%时,导电性能更好。 这为超细银粉在实际中的应用提供重要数据和有益参考。     

Co-WC复合电极在碱性介质中的电催化析氢性能

Co-WC复合电极在碱性介质中的电催化析氢性能