中国贮氢材料和镍氢电池新进展

介绍了中国贮氢材料研究的新进展,贮氢材料的研制主要集中在常规贮氢材料,非晶态贮氢材料,薄膜贮氢材料及贮氢材料的表面处理等方面。在其诸多应用中,镍/金属氢化电池的研究正在走向产业化。

绿色电源——镍/氢充电电池

大街小巷,川流不息的汽车冒出一股股呛人的黑烟,给拥挤的城镇带来可怕的污染和危害。改变这一现状的根本措施,只有推广电动汽车,如今全球汽车巨人都在为实现这个梦想而拚搏。有朝一日,这一梦想成为现实,将使全世界价值5000亿美元的汽车工业发生彻底的变化。攻克电动汽车难关的关键技术是动力电池。传统的铅酸和镍/镉充电电池能量密度低,动力性能很难满足电动汽车的需求。而新兴的镍金属氢化物充电电池(简称镍/氢电池),则具备满足电动汽车动力和里程的基本要求。1994年3月,由美国密西根州奥沃尼克电池公司和通用汽车公司联合推出的镍/氢电池为动力的“Geo Metzo”电动汽车,以每小时65英里的不间断时速,赢得了125英里电动汽车竞赛的桂冠,迈出了电动汽车走向实用化的新步伐。

Electrochemical hydrogen storage characteristics of as-cast and annealed La_(0.8-x)Nd_xMg_(0.2)Ni_(3.15)Co_(0.2)Al_(0.1)Si_(0.05)(x=0-0.4)alloys

The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure, as well as some residual phase LaNi3 and NdNi5. The discharge capacity and high rate discharge ability （HRD） of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys （x=0.3） yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate （S100） at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.

Experiment Study on the Ending Criteria of Charge and Discharge of Nickel-Hydride Battery

Charge and discharge characteristics of Ni/MH batteries are investigated with experiments. During battery’s working, the voltage, capacity, temperature and internal resistance were recorded, corresponding curves were depicted. Variations of the aforementioned four parameters are differently obvious. Ending criteria of charge and discharge of Ni/MH batteries are discussed on the basis of the curves. Voltage, capacity and temperature of a battery can be used as ending criteria during charge. When discharge takes place, voltage, capacity and internal resistance can be chosen as ending criteria. As a whole, capacity is more suitable for being used as ending criteria of charge and discharge than the other three parameters. At last, the capacity of a battery is recommended to be ending criteria of charge and discharge. The conclusions will provide references to different capacity Ni/MH batteries for electric vehicles.

Phase structure and electrochemical properties of La_(0.7)Ce_(0.3)Ni_(3.75)Mn_(0.35)Al_(0.15)Cu_(0.75-x)Fe_x hydrogen storage alloys

La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-xFex （x=0-0.20） hydrogen storage alloys were synthesized by induction melting and subsequent annealing treatment, and phase structure and electrochemical characteristics were investigated. All alloys consist of a single LaNi5 phase with CaCu5 structure, and the lattice constant a and the cell volume （V） of the LaNi5 phase increase with increasing x value. The maximum discharge capacity gradually decreases from 319.0 mA？h/g （x=0） to 291.9 mA？h/g （x=0.20） with the increase in x value. The high-rate dischargeability at the discharge current density of 1200 mA/g decreases monotonically from 53.1% （x=0） to 44.2% （x=0.20）. The cycling stability increases with increasing x from 0 to 0.20, which is mainly ascribed to the improvement of the pulverization resistance.

Effects of spinning rate on structures and electrochemical hydrogen storage performances of RE-Mg-Ni-Mn-based AB_2-type alloys

La was partially substituted by Ce with the aim of improving the electrochemical hydrogen storage performances ofLa1–xCexMgNi3.5Mn0.5 (x=0, 0.1, 0.2, 0.3, 0.4) alloys, and melt spinning technology was adopted to fabricate the alloys. Theidentification of XRD and SEM reveals that the experimental alloys consist of a major phase LaMgNi4 and a secondary phase LaNi5.The growth of spinning rate results in that the lattice constants and cell volume increase and the grains are markedly refined. Theelectrochemical measurement shows that the as-cast and spun alloys can obtain the maximum discharge capacities just at the firstcycle without any activation needed. With the increase of spinning rate, the discharge capacities of the alloys first increase and thendecline, whereas their cycle stabilities always grow. Moreover, the electrochemical kinetic performances of the alloys first increaseand then decrease with spinning rate growing.

An investigation on electrochemical performances of as-cast and annealed La_(0.8)Mg_(0.2)Ni_(3.3)Co_(0.2)Si_x(x=0-0.2)alloy electrodes for Ni/MH battery application

The La-Mg-Ni-based A2B7-type La0.5Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The influences of the additional silicon and the annealing treatment on the structure and electrochemical performances of the alloys were investigated systemically. Both of the analyses of XRD and SEM reveal that the as-cast and annealed alloys are of a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as one minor phase LaNi3. The addition of Si and annealing treatment bring on an evident change in the phase abundances and cell parameters of （La, Mg）2Ni7 and LaNi5 phase for the alloy without altering its phase structure. The phase abundances decrease from 74.3% （x=0） to 57.8% （x=0.2） for the （La, Mg）2Ni7 phase, and those of LaNi5 phase increase from 20.2% （x^0） to 37.3% （x=0.2）. As for the electrochemical measurements, adding Si and performing annealing treatment have engendered obvious impacts. The cycle stability of the alloys is improved dramatically, being enhanced from 80.3% to 93.7% for the as-annealed （950 ℃） alloys with Si content increasing from 0 to 0.2. However, the discharge capacity is reduced by adding Si, from 399.4 to 345.3 mA.h/g as the Si content increases from 0 to 0.2. Furthermore, such addition makes the electrochemical kinetic properties of the alloy electrodes first increase and then decrease. Also, it is found that the overall electrochemical properties of the alloys first augment and then fall with the annealing temperature rising.

Preparation and Electrochemical Performances of Nickel Metal Hydride Batteries with High Specific Volume Capacity

Cylindrical nickel metal hydride （Ni-MH） battery with high specific volume capacity was prepared by using the oxyhydroxide Ni（OH）2 and AB5 type hydrogen storage alloy and adjusting the designing parameters of positive and negative electrodes. The oxyhydroxide Ni（OH）2 was synthesized by oxidizing spherical β-Ni（OH）2 with chemical method. The X-ray diffraction （XRD） patterns and the Fourier transform infrared （PT-IR） spectra indicated that 7-NiOOH was formed on the oxyhydroxide Ni（OH）2 powders, and some H2O molecules were inserted into their crystal lattice spacing. The battery capacity could not be improved when the oxyhydroxide Ni（OH）2 sample was directly used as the positive active materials. However, based on the conductance and residual capacity of the oxyhydroxide Ni（OH）2 powders, AA size Ni-MH battery with 2560 mA.h capacity and 407 W·h·L^-1 specific volume energy at 0.2C was obtained by using the commercial spherical β-Ni（OH）2 and AB5-type hydrogen-storage alloy powders as the active materials when 10% mass amount of the oxyhydroxide Ni（OH）2 with 2.50 valence was added to the positive active materials and subsequently the battery designing parameters were adjusted as well. The as-prepared battery showed 70% initial capacity after 80 cycles at 0.5C. The possibility for adjusting the capacity ratio of positive and negative electrodes from 1 ： 1.35 to 1 ： 1.22 was demonstrated preliminarily. It is considered the as-prepared battery can meet the requirement of some special portable electrical instruments.

Effect of Sn substitution for Co on microstructure and electrochemical performance of AB_5 type La_(0.7)Mg_(0.3)Al_(0.3)Mn_(0.4)Co_(0.5-x)Sn_xNi_(3.8)(x=0-0.5) alloys

The effects of substitution of Sn for Co on the microstructure, hydrogen storage and electrochemical discharge capacity of La0.7Mg0.3Al0.3Mn0.4Co0.5-xSnxNi3.8 （x=0, 0.1, 0.2, 0.3 and 0.5） alloys were investigated using X-ray diffraction （XRD）, pressure composition isotherm （PCT） and electrochemical discharge cycle. XRD, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） tests showed that all of alloys are mainly composed of LaNi5 and MgNi2 phases, but when increasing the content of Sn in alloys, the LaNiSn phase appears and microstructure is refined. The PCT showed that increasing substitution of Sn for Co results in decrease of the maximum hydrogen storage capacity from 1.48% （x=0） to 0.85% （x=0.5）. The electrochemical tests indicated that the maximum discharge capacity decreases from 337.1 mA-h/g （x=0） to 239.8 mA.h/g （x=0.5）; however, the discharge capacity retention at the 100th cycle increases from 70.2% （x=0） to 78.0% （x=0.5）.