NiO/AC非对称超级电容器的研究

通过热处理球形Ni（OH）2得到NiO粉末，将其作为正极与活性炭（AC）负极组装成非对称超级电容器，用恒流充放电测试分析了超级电容器的电容特性。讨论了正负极活性物质比例、充放电电流和热处理时间对超级电容器比电容量、内阻的影响。结果表明：正负极活性物质比为1：3，工作电流密度为200mA／g，当Ni（OH）2的热处理时间为2h，充电电压为1．3V时，超级电容器的双电极比电容量可达71．5F／g。     

充放电速率对聚吡咯稳定性的影响

聚吡咯（PPy）作为电池、超电容、传感器以及人工肌肉的电极材料国内外已经开展了较多的研究工作,但PPy的稳定性一直是制约其商业化的关键因素．本文研究了在1M的Na2SO4和1M的NaCl的电解液体系中充放电速率对PPy电极稳定性的影响．结果表明扫描速率越高PPy电极的稳定性越好,这是由于在高扫描速率下,PPy电极的比容量相对较小,即在PPy电极掺杂／脱掺杂的过程中进出PPy骨架的阴离子较少,PPy体积变化相应较小,较小的体积变化在PPy反复的掺杂／脱掺杂的过程中必然对PPy骨架造成的损伤较小,这是其稳定性好的主要原因．     

Preparation and electrochemical performance of spherical Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for Li-ion batteries

Fe₃O₄ nano-powder was prepared by the hydrothermal method. The structure and morphology of the product were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The as-prepared powder has regularly spherical morphology, and the average size of product is about 25 nm. The possible application use of this material as the active mass of anode for rechargeable Li batteries was examined by cyclic voltammeter (CV), galvanostatic charge/discharge. The experimental results showed that this material exhibited large specific capacity at the first cycle, and the discharge and charge capacity retention of this electrode are 37.04% and 48.76%, respectively. Furthermore, the impedance change of Fe₃O₄ electrode under different cycle number and potential was examined.     

Improvement of Lithium Interface Stability with 1,4-dioxane Pretreatment

1,4-dioxane （DOA） was originally used to pretreat the lithium metal electrode in order to improve its interface stability. Electrochemical impedance spectra （EIS） measurements reveal that with DOA pretreatment, lithium electrode has a low and stable interfacial resistance during the storage in electrolyte for a long time. And it is also found that the pretreated lithium electrode has an improved interfacial performance in repeated charge/discharge cycles. Furthermore, it is proved by SEM that the pretreated one has smooth morphology after long-time storage or repeated charge/discharge cycles. Consequentially, because of more stable interface characteristics of lithium electrode, the rechargeable lithium cell with DOA pretreated lithium anode has an obviously enhanced discharging performance and a better cycleability, compared with that of the cell using the untreated lithium anode.     

Application of thermal electrochemical equation to metal-hydride half-cell system

1 INTRODUCTIONNickel-metal hydride ( Ni/ MH) battery be-came the principal power of electronic vehicle be-cause of its excellent characteristics such as highenergy density , high power , no memory effect ,long service life and wide temperature perform-ance . The hydrogen storage alloy is the key mate-rial of Ni/ MH dynamical battery , a mass of re-search work such as the technique of preparation,the performance of thermodynamics , kinetics andelectrochemistry were accomplished in recenty…     

阳极溶出伏安法测定酒中微量锌

研究了阳极溶出伏安法测定微量至痕量锌的实验条件和有关的影响因素。在pH为5～6的NH_4CI—HC1支持电解质溶液中,-1.3V的富集电位下,以铂基汞膜电极为工作电极,大面积银汞膜电极为参比电极,用该方法可直接测定酒样中微量至痕量的锌。检出下限达0.2ng/ml,回收率为98～106％。试样中辞含量为2～300ng/ml时,伏安曲线的峰高与锌含量呈良好的线性关系。实验结果表明,该方法可靠易行。     

1,3-二氧戊环对锂的表面改性机理

为研究预处理液对二次金属锂电极的表面改性机理,采用1,3-二氧戊环作为预处理液,对锂电极进行浸泡处理,然后与LiCoO2组装成扣式电池.测试电池的循环性能和放电性能,并对循环到第10次和第70次的电池在不同放电电压下进行电化学阻抗谱(EIS)研究,提出一种合理的等效电路模型分析锂电极各部分阻抗的变化.结果表明,用13,-二氧戊环处理可使锂电极性能得到较大提高.EIS分析表明,处理后生成的SEI膜结构更稳定,而且与锂基体的界面相容性更好,使电子转移更容易进行.锂负极在循环过程中性能下降的主要原因是其表面膜电阻和电荷传递电阻越来越大,导致锂离子在SEI膜中的迁移阻力增大,电子转移阻力也增大.     

La1-xCexNi3.54Co0.78Mn0.35Al0.32贮氢合金相结构和电化学性能的研究

采用真空电弧熔炼和热处理方法制备了La1-xCexNi3.54Co0.78Mn0.35Al0.32(x=0.1,0.2,0.3,0.4,0.5,0.6)贮氢合金.X射线衍射(XRD)分析表明,合金含有单一CaCu5型六方结构相.电化学性能测试表明,随着x的增加,合金的最大放电容量从348.1mAh/g(x=0.1)单调地减小到310.1 mAh/g(x=0.6);HRD1200先从28.6%(x=0.1)增加到65.4%(x=0.5)然后降低到60.1%(x=0.6),归因于合金表面的电催化活性和合金体内氢原子扩散速率均随x的增大先增大后减小.     

Performance of a combined capacitor based on ultrafine nickel oxide／carbon nanotubes composite electrodes

A new sol-gel process for the preparation of ultrafine nickel hydroxide electrode materials was developed. The composite electrodes consisting of carbon nanotubes and Ni(OH)2 were developed by mixing the hydroxide and carbon nanotubes together in different mass ratios. In order to enhance energy density, a combined type pseudocapacitor/electric double layer capacitor was considered and its electrochemical properties were characterized by cyclic voltammetry and dc charge/discharge test. The combined capacitor shows excellent capacitor behavior with an operating voltage up to 1.6 V in KOH aqueous electrolyte. Stable charge/discharge behaviors were observed with much higher specific capacitance values of 24 F/g compared with that of EDLC (12 F/g) by introducing 60% Ni(OH)2 in the anode material. By using the modified anode of a Ni(OH)E/Carbon nanotubes composite electrode, the specific capacitance of the cell was less sensitive to discharge current density compared with that of the capacitor employing pure nickel hydroxide as anode. The combined capacitor in this study exhibits high energy density and stable power characteristics.     

碳微米螺旋纤维的电化学特性研究

用碳螺旋纤维作锂离子电池的电极,选择金属锂片作为对电极和参比电极,系统地测量其极化过程中的充放电曲线、循环性能以及电化学阻抗谱.结果表明：首次放电比容量为304.06mAh/g,首次充电比容量为184.87mAh/g,不可逆比容量为119.19mAh/g;循环实验显示,该材料第150周放电比容量达到170mAh/g,为第2周的80%,循环性能良好,这与碳螺旋纤维的大比表和中空结构密切相关;首次放电阻抗谱显示,当电极电位位于1.2～0.6V时,电解液与螺旋纤维间的固体电解质相界面膜（简称SEI膜）开始生长,所形成的SEI膜性质稳定,这也为维护循环稳定性提供有力保障.     

Electrochemical Performance and EIS Analysis of Commercial Lithium-Ion Battery

Degradation behavior is the main technical problem in the field of commercial application of lithium-ion batteries.According to the characteristics of voltage,discharge capacity and inner resistance during the charge/discharge process of commercial lithium-ion batteries of mobile telephone,degradation analysis and related mechanisms are put forward and discussed in the paper.The impedance spectra of prismatic commercial lithium-ion batteries are measured at various state of charge after different charge/discharge cycles.The measured impedance spectra are discussed with a proposed equivalent circuit.Results indicated that the structure change of electrode materials or swell and shrink of crystal lattice,decompose of electrolyte,dissolution of active materials and solid electrolyte interphase film formation are the main reasons leading to the capacity degradation.     

超级电容器PANI/MnO2 复合材料电极的制备及性能研究

通过回收废旧三元锂电池正极材料中的Mn 制备超级电容器PANI/MnO₂ 复合电极材料, 实现废旧材料的资源化, 符合绿色化学的发展要求。主要探索了两种不同氧化剂(KMnO₄ 和APS) 对PANI/MnO₂ 复合材料形貌和电化学性能的影响, 由实验结果可知, 在KMnO₄ 氧化条件下制备的具有空隙的针棒状复合材料PANI/MnO₂ -1 的电化学性能明显略优。PANI/MnO₂ -1 作为电极时的比电容可达2 183 F/g, 充放电100 圈后比电容仍具有初始值的60.81%, 循环稳定性较好, 是一种性质优良的超级电容器电极材料。结果表明实验设计的废旧三元锂电池回收再利用方法切实可行, 为超级电容器PANI/MnO₂ 复合材料电极的制备提供了新的研究思路。     

四氧化三锰/石墨烯超级电容器的制备及分析

为了最大程度上保留石墨烯的晶格结构以提高其电导并简化过渡金属氧化物与石墨烯复合物的制备过程,通过氢电弧放电和简易的高温处理成功制备得到四氧化三锰/石墨烯纳米复合材料,并将其用作超级电容器的电极.通过XRD、Raman光谱和TEM对产物的形貌、结构及成分进行了表征.电化学测试结果表明,由该材料制得的超级电容器具有良好的电容性质、出色的电化学稳定性(循环3 000圈后大约保持96%)以及较低的等效串联电阻.同时,四氧化三锰的掺入可使其比电容提高到纯石墨烯电极的3倍.因此,此方法为制备以新型石墨烯复合过渡金属氧化物作为高性能超级电容器电极的研究提供了新思路.     

不同放电深度下LaNi3.8Co0.6Mn0.3Al0.3合金的电化学行为研究

为了分析储氢合金放电过程中的电化学反应与动力学变化规律,采用电化学交流阻抗分析方法研究 La-Ni3.8Co0.6Mn0.3Al0.3合金电极在不同放电深度下的电化学行为.结果表明:随着放电深度的增加,电极表面活性氢覆盖面积S 及内部金属颗粒间接触电阻Rpp逐渐降低,即电极的导电性增加;此外,交换电流密度Io也随放电深度增加而增大,意味着电极表面反应速率加快,同时氢扩散系数 DH 明显降低;合金电极动力学在放电前期主要由电极表面反应速率控制,后期由电极中氢原子在合金颗粒内部的氢扩散系数控制.     

MLNi_4Cr和MLNi_4Si贮氢电极的性能

利用交流阻抗、循环伏安及扫描电镜（ＳＥＭ）观察等方法，测定了ＭＬＮｉ４和ＭＬＮｉ４Ｓｉ（ＭＬ：富镧混合稀土金属）贮氢电极的性能，并对两电极性能差别的原因进行了分析和讨论．结果表明，ＭＬＮｉ４Ｃｒ电极比ＭＬＮｉ４Ｓｉ电极易活化、放电容量大、过电位小以及快速放电能力强；而ＭＬＮｉ４Ｓｉ电极具有较好的循环充放电特性．     

MLNi_4Cr和MLNi_4Si贮氢电极的性能

利用交流阻抗、循环伏安及扫描电镜（ＳＥＭ）观察等方法，测定了ＭＬＮｉ４和ＭＬＮｉ４Ｓｉ（ＭＬ：富镧混合稀土金属）贮氢电极的性能，并对两电极性能差别的原因进行了分析和讨论．结果表明，ＭＬＮｉ４Ｃｒ电极比ＭＬＮｉ４Ｓｉ电极易活化、放电容量大、过电位小以及快速放电能力强；而ＭＬＮｉ４Ｓｉ电极具有较好的循环充放电特性．     

CuS Electrode for All-pH Electrolyte in Aqueous Batteries

用于水系电池中全pH电解质的CuS电极

杨亮亮^{1, 3}, 崔芒伟^1,3, 刘清江^{1, 3}, 雷浩^{1, 3} ，黄燕^1,2,3

(1. 哈尔滨工业大学（深圳） 索维奇智能材料实验室，材料科学与工程学院，深圳 518055；2. 哈尔滨工业大学 先进焊接与连接国家重点实验，哈尔滨 150001；3. 哈尔滨工业大学（深圳） 深圳市柔性印刷电子技术重点实验室，深圳 518055）

中文说明：

水系电池以其优异的安全性、经济性、环境友好性和高离子导电性成为替代锂离子电池的有力竞争者。然而，电池中电解液的pH值通常会影响电池的电化学性能，甚至影响电池的正常运行。因此，开发能够在各种pH环境下工作的电极材料至关重要。本文采用水热法和硫化处理成功制备了硫化铜纳米片。它可以存储和传输非金属和金属离子以及具有高电荷半径比的多价离子，同时在各种pH条件下正常工作。特别是，CuS电极在碱性条件下具有高容量（900 mAh g-1）、高倍率性能以及超长的放电平台，该平台贡献了总容量的80%。

关键词：水系电池；硫化铜；全pH电解质

     

Preparation and properties of pitch carbon based supercapacitor

Using the mesophase pitch as precursor, KOH and CO2 as activated agents, the activated carbon electrode material was fabricated by physical-chemical combined activated technique for supercapacitor. The influence of activated process on the pore structure of activated carbon was analyzed and 14 F supercapacitor with working voltage of 2.5 V was prepared. The charge and discharge behaviors, the properties of cyclic voltammetry, specific capacitance, equivalent serials resistance (ESR), cycle properties, and temperature properties of prepared supercapacitor were examined. The cyclic voltammetry curve results indicate that the carbon based supercapacitor using the self-made activated carbon as electrode materials shows the desired capacitance properties. In 1 mol/L Et4NBF4/AN electrolyte, the capacitance and ESR of the supercapacitor are 14.7 F and 60 m?, respectively. The specific capacitance of activated carbon electrode materials is 99.6 F/g; its energy density can reach 2.96 W·h/kg under the large current discharge condition. There is no obvious capacitance decay that can be observed after 5000 cycles. The leakage current is below 0.2 mA after keeping the voltage at 2.5 V for 1 h. Meanwhile, the supercapacitor shows desired temperature property; it can be operated normally in the temperature ranging from -40 ℃ to 70 ℃.     

聚乙酰苯胺/氧化石墨烯纳米复合材料制备及其超级电容性能

采用改进的Hummers方法制备氧化石墨,在乙醇溶液中超声分散120 min得到氧化石墨烯悬浮液。采用滴涂法在玻碳电极表面得到氧化石墨烯薄膜,通过电化学技术在氧化石墨烯薄膜上沉积得到聚乙酰苯胺纳米线,成功制备了聚乙酰苯胺/氧化石墨烯纳米复合材料(PAANI/GO)。利用扫描电镜、循环伏安法和恒电流充放电测试技术对合成材料的形貌和充放电性能进行表征和测试。结果表明,直径为80 nm的聚乙酰苯胺纳米线均匀分散在氧化石墨烯表面,制备的复合材料在1 mol/L高氯酸溶液中,当循环伏安扫速为10 m V/s时,可以获得706 F/g的比电容,PAANI的比电容为285 F/g。聚乙酰苯胺/氧化石墨烯纳米复合材料具有优异的充放电稳定性,当恒电流为1A/g时,循环充放电1 000次比电容是初始值的90%。     

液晶模板法制备Co3O4分级多孔结构薄膜和赝电容性能研究

采用液晶模板法制备Co3O4纳米薄膜,用循环伏安法和恒流充放电测试方法,表征分析其微观结构和电化学性能。结果表明：Co3O4薄膜是多晶体,呈分级多孔结构,该结构有利于电子和离子的扩散,可显著改善超级电容器的比电容,增强电容保持能力,是一种优良的超级电容器电极材料。