Effects of ball milling on the physical and electrochemical characteristics of nickel hydroxide powder

Nickel hydroxide powder was modified by the method of ball milling, and the physical properties of both the ball-milled and un-milled nickel hydroxide were characterized by scanning electron microscopy, specific surface area, particle size distribution and X-ray diffraction. It was found that the ball milling processing could obviously increase the surface area, decrease the particle and crystallite size, and reduce the crystallinity of β-Ni(OH)₂, which was advantageous to the improvement of the electrochemical activity of nickel hydroxide powder. Electrochemical performances of pasted nickel electrodes using the ball-milled nickel hydroxide as an active material were investigated, and were compared with those of the electrodes prepared with the un-milled nickel hydroxide. Charge/discharge tests showed that the ball-milled nickel hydroxide electrodes exhibited better performances in the charging efficiency, specific discharge capacity, active material utilization and discharge voltage. The improvement of the performances of β-Ni(OH)₂ through ball milling could be attributed to the better reaction reversibility, higher coulombic efficiency, higher oxygen evolution potential and lower electrochemical impedance, as indicated by the cyclic voltammetry and electrochemical impedance spectroscopy studies. Thus, ball milling was an effective method to modify the physical properties and enhance the electrochemical performances of nickel hydroxide powder for the active material of rechargeable alkaline nickel batteries.     

Performance improvement of pasted nickel electrodes with multi-wall carbon nanotubes for rechargeable nickel batteries

Carbon nanotubes (CNTs) were employed as a functional additive to improve the electrochemical performance of pasted nickel-foam electrodes for rechargeable nickel-based batteries. The nickel electrodes were prepared with spherical β-Ni(OH)₂ powder as the active material and various amounts of CNTs as additives. Galvanostatic charge/discharge cycling tests showed that in comparison with the electrode without CNTs, the pasted nickel electrode with added CNTs exhibited better electrochemical properties in the chargeability, specific discharge capacity, active material utilization, discharge voltage, high-rate capability and cycling stability. Meanwhile, the CNT addition also lowered the packing density of Ni(OH)₂ particles in the three-dimensional porous nickel-foam substrate, which could lead to the decrease in the active material loading and discharge capacity of the electrode. Hence, the amount of CNTs added to Ni(OH)₂ should be optimized to obtain a high-performance nickel electrode, and an optimum amount of CNT addition was found to be 3 wt.%. The superior electrochemical performance of the nickel electrode with CNTs could be attributed to lower electrochemical impedance and less γ-NiOOH formed during charge/discharge cycling, as indicated by electrochemical impedance spectroscopy and X-ray diffraction analyses. Thus, it was an effective method to improve the electrochemical properties of pasted nickel electrodes by adding an appropriate amount of CNTs to spherical Ni(OH)₂ as the active material.     

氢氧化镍电极的修饰及电化学性能的研究

镍系列二次电池的正极活性物质Ni（OH）2的晶型和镍电极的制备工艺对电池的性能具有较大的影响。文章以镍-氢电池作为对象,着重研究作为电池正极的氢氧化镍电极。通过不同的方法制备电极的活性物质Ni（OH）2,以Co、Zn和稀土作为掺杂剂对电极进行修饰,并对不同掺杂方式构成的电池进行了测试。用金相显微镜来观察Ni（OH）2的外观、颗粒大小;通过恒电流放电曲线比较各电极的放电性能,并通过XRD谱图了解样品的晶型结构。电池性能测试结果表明：采用配位沉淀法制备的Ni（OH）2晶体为最佳;在添加剂方面,Zn、Co、Sm均对镍电极的电化学性能影响较大。     

非晶相氢氧化镍电极材料的研究进展

非晶态材料原子排列无序性强、结构缺陷多,内部含有大量配位不饱和原子和表面活性中心,是理想的高性能电极材料.本文综述了非晶相氢氧化镍电极材料的制备方法,描述了非晶相氢氧化镍作为电极活性材料的电化学特性.提出了非晶相氢氧化镍进一步的研究方向.     

非晶态氢氧化镍复合碳纳米管电极材料的电化学性能

采用快速冷冻化学共沉淀法制备非晶态Ni(OH)2粉体,将其作为电化学活性物质复合碳纳米管合成镍电极材料,研究了其电化学性能. 结果表明,加入碳纳米管有效减少了镍电极的电荷转移电阻,增大了电极反应过程的质子扩散系数. 复合0.5%(w)碳纳米管合成的非晶态氢氧化镍电极材料在1 C充放电制度下,放电终止电压为1.0 V时,其放电比容量高达336.5 mA×h/g,放电中值电压为1.251 V,充放电循环30次,放电比容量保持率为96.74%,表现出较好的高倍率充放电性能.     

Cyclic voltammetric studies of pasted nickel hydroxide electrode microencapsulated by cobalt

Spherical nickel hydroxide microencapsulated by cobalt has been used as the electrochemically active material in pasted-type nickel electrodes of rechargeable alkaline batteries. Cobalt coating on the surface of nickel hydroxide particles can be converted to CoOOH during charge. Well distributed CoOOH forms the conductive network on the surface of nickel hydroxide particles, thereby leading to higher utilization of active material. Cyclic voltammetric studies suggest that nickel hydroxide microencapsulated by cobalt has better reversibility of the Ni(OH)2/NiOOH redox couple, greater discharge capacity and higher oxygen evolution overpotential than nickel hydroxide with added cobalt metal powder as a conductor. The mechanism of the electrode reaction is still found to be controlled by proton diffusion, and the proton diffusion coefficient is 1. 2×10–9cm2s–1.     

PVA基碱性聚合物电解质Ni(OH)2/AC超级电容器的电化学性能

Polyvinyl alcohol(PVA)-sodium polyacrylate(PAAS)-KOH-H₂O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method.Polymer Ni(OH)₂/activated carbon(AC) hybrid supercapacitors with different electrode active material mass ratios(positive to negative) were fabricated using this alkaline polymer electrolyte,nickel hydroxide positive electrodes,and AC negative electrodes.Galvanostatic charge/discharge and electrochemical impedance spectroscopy(EIS) methods were used to study the electrochemical performance of the capacitors,such as charge/discharge specific capacitance,rate charge/discharge ability,and charge/discharge cyclic stability.Experimental results showed that with the decreasing of active material mass ratio m(Ni(OH)₂)/m(AC),the charge/discharge specific capacitance increases,but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.     

Dynamic monitoring of structural changes in nickel hydroxide electrodes during discharge in batteries

The nickel hydroxide electrode is used as the positive plate of many rechargeable battery systems such as the nickel/cadmium, nickel/hydrogen, and nickel/metal hydrides. The electrochemical energy storage in the nickel hydroxide electrodes is related to the reversible characteristics of the redox couple nickel hydroxide/ox hydroxide. In the present work we describe the use of the electrochemical impedance spectroscopy (EIS) technique as a tool to characterize the dynamic behaviour of nickel hydroxide electrodes at different states of discharge (SOD) in KOH 7 M electrolytic solutions. The parameter identification procedure allows the estimation of the active area per unit volume, the solution conductivity as well as diffusion and kinetic constants related to the process, that represent very important parameters to evaluate the electrode performance.     

Physical and electrochemical characteristics of nanostructured nickel hydroxide powder

Nanostructured nickel hydroxide powder has been synthesized by a chemical precipitation method with the aid of ultrasound radiation, and the physical properties of the synthesized material were characterized by scanning electron microscopy, specific surface area, X-ray diffraction and differential scanning calorimetry. It was found that nanostructured nickel hydroxide was crystalline -Ni(OH)₂ with a nanocrystalline and nanoporous surface structure. The crystallite sizes of nanostructured -Ni(OH)₂ along the c- and a-axis were 2.5 and 2.3 nm, respectively, as calculated from (001) and (100) X-ray diffraction peaks. In comparison with spherical -Ni(OH)₂ which has now been widely used as the active material for pasted nickel electrodes, nanostructured -Ni(OH)₂ possessed a smaller crystallite size, more structural defects, a larger lattice parameter of c₀, a higher specific surface area and lower thermal decomposition temperature. These physical characteristics were advantageous to the improvement of electrochemical activity of the nanostructured nickel hydroxide powder. Studies indicated that the filling property and flowability of nanostructured -Ni(OH)₂, which were characterized by the measurements of tapping density and angle of repose, were inferior to those of spherical -Ni(OH)₂. Pasted nickel electrodes with a porous nickel-foam substrate were prepared using a mixture of the nanostructured and spherical Ni(OH)₂ powders as the active material. Charge/discharge tests showed that the addition of an appropriate amount of nanostructured Ni(OH)₂ powder to spherical Ni(OH)₂ powder could enhance the specific discharge capacity and high-rate capability of the pasted nickel electrodes. This enhancement could be attributed to a lowered electrochemical reaction impedance for the nickel electrode with the addition of nanostructured Ni(OH)₂ relative to the electrode without nanostructured Ni(OH)₂.     

硫酸钴对镍电极电化学性能的影响

研究了CoSO4添加剂对镍电极和镍氢电池电化学性能的影响，镍电极反应活性和可逆性随CoSO4添加量增加而增大，CoSO4经过3-5次充放电循环后逐渐转变为CoOOH，与CoO添加剂的变化趋势一致。采用含CoSO4的镍电极与金属氢化物电极组装成MH／Ni电池，在第150次循环之前，电池放电容量一直随着循环次数的增加而增加，经过250次循环后，容量保持率仍高达95％：CoSO4添加量分别为11.2％、18.7％和30.0％时，相应的镍电极最高放电比容量分别为270、280和287mAh／g。由于CoSO4具有制备工艺简单、不容易氧化、成本低等特点，因此可替代CoO降低MH／Ni电池的制造成本。     

稀土La(Ⅲ)掺杂非晶态氢氧化镍的电化学性能

采用微乳液快速冷冻沉淀法制备出稀土La(Ⅲ)掺杂非晶态Ni(OH)2粉体材料,对样品粉体的微结构及形态进行了表征分析,同时将样品作为活性物质合成电极材料,组装成碱性MH-Ni模拟电池,测试其电化学性能。结果表明,掺杂6%La(Ⅲ)样品材料微结构无序性强,质子缺陷较多。将所制备的样品在80 mA/g恒电流充电5.5 h,40 mA/g恒电流放电,终止电压为1.0 V的充放电制度下,其放电平台达到1.256 V,放电比容量为317.1 mAh/g,充放电循环30次放电比容量衰减仅为3.943%,具有较好的电化学稳定性和循环可逆性。     

Performance improvement of pasted nickel electrodes with an addition of ball-milled nickel hydroxide powder

Spherical β-Ni(OH)₂ was modified by a low-cost method of normal ball milling (NBM), and the physical properties of both ball-milled and un-milled Ni(OH)₂ were characterized by transmission electron microscopy, specific surface area, particle size distribution and X-ray diffraction. It was found that NBM could obviously increase the surface area, decrease the particle and crystallite size, and reduce the crystallinity of β-Ni(OH)₂, which were advantageous to the improvement of the electrochemical activity of Ni(OH)₂. NBM also lowered the packing density and flowability of Ni(OH)₂, as revealed by the measurements of tapping density and angle of repose. Electrochemical performances of pasted nickel electrodes with an addition of ball-milled Ni(OH)₂ to spherical Ni(OH)₂ as the active material were investigated, and were compared with those of the pure spherical Ni(OH)₂ electrodes. Charge/discharge tests showed that ball-milled Ni(OH)₂ addition could enhance the charging efficiency, specific discharge capacity, discharge voltage and high-rate capability of the electrodes. This performance improvement could be attributed to a more compact electrode microstructure, better reaction reversibility and lower electrochemical impedance, as indicated by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Thus, it was an effective method to modify the microstructure and improve the electrochemical properties of pasted nickel electrodes by adding an appropriate amount of ball-milled Ni(OH)₂ to spherical Ni(OH)₂ as the active material.     

Study of the performance of secondary alkaline pasted zinc electrodes

Calcium zincate was prepared by a chemical coprecipitation method and characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical performance of pasted zinc electrodes with bismuth and calcium additives was investigated by the charge–discharge method. The addition of metallic bismuth powder improves the discharge performance of zinc electrodes due to the formation of an electronic conduction matrix. The calcium-containing zinc electrodes showed higher discharge capacity, less shape change and longer cycle lifetime. Moreover, zinc electrodes using calcium zincate as active material show better electrochemical performance than those with the physical mixture of zinc oxide and calcium hydroxide.     

Ni(OH)2/活性炭复合材料在超级电容器中的应用

用化学沉淀法在活性炭(AC)表面和微孔内掺杂不同量的氢氧化镍,制备了氢氧化镍-活性炭[Ni(OH)2-AC]复合材料. 用X射线衍射(XRD)和氮气吸附等温线等对活性炭和复合材料进行表征,结果表明,所制材料为b-Ni(OH)2-AC复合材料. 对不同掺杂量的b-Ni(OH)2-AC复合材料的电化学性能进行了研究,循环伏安、恒流充放电实验表明,少量氢氧化镍掺入活性炭表面和微孔中,所得材料的比电容较活性炭有所提高,并具有良好的充放电性能;当氢氧化镍的掺入量为6%(w)时,所制备的超级电容器单电极表现出优良的电化学性能. 以活性炭电极作负极,复合材料作正极制成复合型超级电容器,循环性能测试发现,掺入6%(w)氢氧化镍的复合材料制成的Ni(OH)2-AC/AC复合型超级电容器比电容高达330.7 F/g,比活性炭(AC/AC)超级电容器比电容(245.6 F/g)提高了34.6%,且Ni(OH)2-AC/AC复合型超级电容器具有更好的循环充放电性能.     

A facile preparation of 3D flower-shaped Ni/Al-LDHs covered by β-Ni(OH)2 nanoplates as superior material for high power application

In the present study, we propose a novel electrode material of β-nickel hydroxide covering nickel/aluminum layered double hydroxides via a facile complexation-precipitation method. The as-obtained materials with 3-dimensional nanostructures are further utilized as highly capable electrode material in nickel-metal hydride batteries. The electrochemical test results demonstrated the β-nickel hydroxide covering nickel/aluminum-layered double hydroxides with 28% of β-nickel hydroxide provided a superior specific capacity value of 452 mA·h·g^-1 in a current density of 5 A·g^-1 using 6 M KOH as electrolyte as compared with other materials. In addition, the optimized sample displays an outstanding cyclic stability along with a huge specific capacity value of 320 mAh·g^-1, and very small decay rate of 3.3% at 50 A·g^-1 after 3000 cycles of charge/discharge test. These indicate that the newly designed material with nanostructures not only provides an efficient contact interface between electrolyte and active species and facilitates the transport of electrons and ions, but also protects the 3-dimensional nickel/aluminum layered double hydroxides, achieving a high specific capacity, fast redox reaction and excellent long-term cyclic stability. Therefore, the β-nickel hydroxide covering nickel/aluminum layered double hydroxides with superior electrochemical performance is predictable to be a gifted electrode material in nickel-metal hydride batteries.     

Gas Recombination in Sealed Ni–MHx Cells

This paper focuses on investigation of gas recombination in a positive-limited-sealed Ni–MH_x cell. The positive electrodes were prepared by electrochemical impregnation of fibrous nickel plaques. The metal hydride negative electrodes were made by pasting the mixture of rare-earth hydrogen storage alloy powders, conducting and binding agents on foamed nickel substrates. The measurement of the positive capacity at different charge times was used to estimate the partial current for oxygen evolution at the same time. The effects of charge rate, electrolyte saturation level and initial state of charge of the positive electrodes on the recombination were investigated in sealed Ni–MH_x cells. By determining the differential capacity of nickel hydroxide electrodes, an improved mathematical model was used to evaluate the gas recombination parameters during charge, overcharge, rest and discharge of the positive-limited-sealed Ni–MH_x cell. The gas recombination during rest, discharge and overdischarge was also examined. The oxygen recombination on the nickel hydroxide electrodes can be neglected due to the consumption of water when the nickel hydroxide electrodes were discharged. The longer overdischarge produced an increase in cell pressure for the sealed Ni–MH_x cell at an electrolyte unsaturated level and the evolving gas can be recombined by a following recharge operation. © 1997 SCI.     

水热法制备氧化钴/泡沫镍材料及电容性能分析

利用简单的水热法制备出不同反应液浓度、不同反应时间以及不同反应温度氧化钴/泡沫镍（CoO/NF）电极，旨在改善氧化钴材料的比电容及稳定性。通过XRD、SEM、TEM、EDS Mapping和BET对其结构和形貌进行了表征，同时在1mol/L氢氧化钾（KOH）电解液中采用循环伏安曲线（CV）、充放电曲线（CP）、循环性能测试、大电流充放电测试以及交流阻抗（EIS）测试研究了其电化学性能。表征结果显示氧化钴均匀地分布在泡沫镍载体表面，且片状结构CoO-8h/NF具有较大的比表面积和多孔特性。在三电极体系中，电化学测试结果显示CoO-8h/NF在1mA/cm²电流密度下表现出最好的电容性能，比电容可以达到930mF/cm²。在10mA/cm²电流密度下对CoO-8h/NF电极进行10000次恒电流充放电测试，循环测试后电极的比电容几乎没有衰减，具有较好的稳定性，是超级电容器比较理想的正极材料。     

Structure and electrochemical properties of nickel hydroxide electrodes with cobalt additives

In this article,cobalt additives are introduced into nickel hydroxide electrodes by two incorporation methods—co-precipitated cobalt hydroxide during the nickel hydroxide synthesis or post-added CoO with nickel hydroxide. The results of X-ray diffraction, cyclic voltammetry, electrochemical impedance spectroscopy, and charge–discharge tests indicate that (i) the diffraction peaks show a decrease in intensity and increase in the half peak breadths for Ni(OH)₂ with co-precipitated cobalt hydroxide; (ii) the electrochemical activity of nickel hydroxide can be improved by both incorporated cobalt and the effects of post-added CoO are more notable; (iii) CoOOH derived from post-added CoO is not stable in the KOH electrolyte when the potential of the Ni(OH)₂ electrode is lowered and its reduction product may be inactive, thus results in an irreversible capacity loss of nickel-metal-hydride battery after over-discharge-state storage.     

High temperature performances of yttrium-doped spherical nickel hydroxide

The regular and yttrium-doped spherical β-phase nickel hydroxides were synthesized by means of chemically co-precipitation. The yttrium-doping with long needle-like nanocrystallites observed by TEM promoted the formation of the spherical nickel hydroxide with the larger diameter of about 5 μm. The discharge capacity of the yttrium-doped spherical nickel hydroxide was measured to be slightly lower than that of the regular spherical nickel hydroxide at room temperature. At temperatures of above 50 °C, however, the discharge capacity of the yttrium-doped nickel hydroxide is much higher than that of the regular spherical nickel hydroxide. The improvement of discharge capacity at elevated temperatures was contributed to the increase of the charge acceptance of yttrium-doped nickel hydroxide. The formation of an yttrium-rich surface layer on nickel hydroxide particles raised the oxygen evolution over-potential, leading to performance improvements of the nickel hydroxide electrode. The improvement of high temperature charge acceptance of yttrium-doped nickel hydroxide remarkably contributed to the high temperature charge-discharge efficiency of the nickel-metal hydride (Ni-MH) batteries with a commercial AAA size.     

Preparation of ordered mesoporous nickel oxide film electrodes via lyotropic liquid crystal templated electrodeposition route

A novel electrochemical route to fabricate ordered mesoporous metal oxide film electrodes has been investigated with particular reference to nickel oxide. Ordered mesoporous nickel oxide films are successfully synthesized by templated electrodeposition of H_I-e nickel hydroxide and followed by heat-treatment in air at various temperatures. The films are characterized physically by thermogravimetry (TG), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The applicability of this film as inexpensive and high-performance supercapacitor electrode material is demonstrated by the electrochemical characterization using cyclic voltammetry (CV) and chronopotentiometry technique. The specific capacitance of the nickel oxide film depends on the annealing temperature, showing a maximum value of 590 F g⁻¹ when the as-deposited film is heat-treated at 250 °C for 1.5 h.