Degradation analysis of nickel／metal hydride battery and its electrodes materials

The results indicate that during charge and discharge, the expansion of Ni(OH)2 crystal, pulverization of MH alloy particles and falling off from current collector are identified as the main causes for deterioration of Ni/MH batteries. Meanwhile, the contact resistance of inner battery increases due to the deterioration of the negative and positive electrode, and these changes lead to increasing battery body temperature and damaging its electrode and separator. The fibre‘s expansion and hole‘s diminishment of battery’s separator after degradation will affect the electrochemical performance and cycle life of Ni/MH batteries.     

Electrochemical performance of nickel／metal hydride batteries under unconventional conditions and degradation analysis

The charge-discharge performance and cycle stability of D size Ni/MH batteries at -20℃, 25℃ and 55℃ were examined. The results show that the decline rate of Ni/MH battery discharge capacity at -20℃ and 55℃ are 12.1% and 13.6% ,and the average discharge voltage decreases by a value of 0.13V and 0.06V respectively,cycling stability declines obviously at various temperatures. The capacity degradation of Ni/MH batteries under low temperature is reversible, belonging to transient degradation and that of high and normal temperatures are not reversible, belonging to permanent degradation. Electrochemical impedance spectroscopy, scanning electron microscope and energy dispersive X-ray analyzer were introduced to study the main causes of cycling deterioration of Ni/MH batteries.     

Effects of iron phthalocyanine on performance of MH／Ni battery

Oxygen evolution causes a high inner pressure during charge and overcharge for MH/Ni battery, and an inappropriate eliminating way of the oxygen in the battery results in accumulation of heat. This is the main obstacle to develop and apply high capability and high power battery. How to reduce the ratio of the chemical catalysis rate to the electric catalysis rate in MH/Ni battery is considered as an urgent question. Iron phthalocyanine(FePc) was chosen as an electrochemical catalyst. The batteries were prepared by adding iron phthalocyanine with different dosages. The inner pressure, the capacity attenuation, the discharge voltage and capacity at high current of these three batteries were compared. The battery with 1 mg FePc in the negative electrode exhibits a good performance.     

Rare earth-Mg-Ni-based hydrogen storage alloys as negative electrode materials for Ni/MH batteries

This review is devoted to new rare earth-Mg-Ni-based (R-Mg-Ni-based) hydrogen storage alloys that have been developed over the last decade as the most promising next generation negative electrode materials for high energy and high power Ni/MH batteries. Preparation techniques, structural characteristics, gas-solid reactions and electrochemical performances of this system alloy are systematically summarized and discussed. The improvement in electrochemical properties and their degradation mechanisms are covered in detail. Optimized alloy compositions with high discharge capacities, good electrochemical kinetics and reasonable cycle lives are described as well. For their practical applications in Ni/MH batteries, however, it is essential to develop an industrial-scale homogeneous preparation technique, and a low-cost R-Mg-Ni-based electrode alloy (low-Co or Co-free) with high discharge capacity, long cycle life and good kinetics.     

稀土-镁-镍基贮氢电极合金的研究进展

具有超结构特征的稀土-镁-镍基贮氢合金作为新一代金属氢化物/镍(MH/Ni)电池负极材料,因其高的放电容量和好的倍率放电性能,是目前贮氢电极合金发展的重点材料之一。本文从材料相结构、贮氢特性和电化学性能之间的关系出发,综述了近年来国内外稀土-镁-镍基AB3型、A2B7型和A5B19型贮氢电极合金的研究进展,为开发兼具高容量和长寿命的新型稀土系贮氢电极合金提供有价值的参考。     

Effects of Mm(NiCoAlMn)_5 hydrogen storage alloy coated with Ni-Co-P alloy by electroless plating on electrochemical properties of hydride electrodes

1　INTRODUCTIONNickel metalhydride (MH Ni)rechargeablebatterieswithhydrogenstoragealloysasthenegativeelectrodematerialhaveattractedincreasingattentionsbecauseofseveralinherentadvantages[16 ] .Sofar ,manymulti component,mischmetal based ,hydro gen storagealloyshavebeendevelopedtomeetthere quirementofhighcyclinglife ;theseincludesubstitu tionofthenickelbyMn ,CoandAl[7] .Thecomposi tionofthealloyisimportant ,andtheeffectsofsur facecompositionandmorphologyarealsosignificant.Micro encapsulat…     

Co-B合金粉体的制备和电化学行为

通过NaBH_4还原CoSO_4溶液制备了Co_(0.68)B_(0.32),Co_(0.55)B_(0.45)和Co_(0.50)B_(0.50)一系列超细非晶态Co-B合金粉体.电化学测试表明,在300 mA/g的高电流密度下,3种合金电极的首次放电容量分别高达510.6,666.4和667.2 mA·h/g,经60次循环后,放电容量仍分别有331.6,379.5和390.5 mA·h/g.3种合金电极还表现出良好的高率放电性能,在1200 mA/g的放电电流密度下,放电容量分别为336.2,373.4和390.1 mA·h/g.较高的B含量有助于提高合金的电化学性能,这是因为B的氧化溶解能提高合金电极的实际电化学反应面积.     

新型负极添加剂对MH/Ni电池性能的影响

用过渡金属氧化物作为ＭＨ／Ｎｉ电池的负极添加剂,研究了它对ＭＨ／Ｎｉ电池容量、放电电压、电池内压和循环性能的影响。加人２％的新型负极添加剂,可以在保证电池容量不受影响的前提下,使ＭＨ／Ｎｉ电池的放电中值电压升高约２０ｎＶ,以１Ｃ倍率电流充电时的最大电池内压减少０．４ＭＰＡ,并显著提高电池循环性能。以１Ｃ倍率快速充放测试徨４００次时,其容量保持率在９０％以上,放电中值电压变１．２１６Ｖ。     

双希夫碱对 AB3 型储氢合金的表面改性研究

目的提高Ni/MH二次电池中AB3型储氢合金负极的充放电性能与动力学性能。方法合成一种双希夫碱作为表面改性剂,添加到AB3型储氢合金La0.73Ce0.18Mg0.09Ni3.20Al0.21Mn0.10Co0.60中,进行表面处理,考察添加不同含量的双希夫碱对合金充放电性能及动力学性能的影响。结果紫外与红外图谱显示,合成了目标双希夫碱。合金添加双希夫碱后,合金的相结构基本没有发生变化。表面处理后的合金与未改性合金相比,最大放电容量从375.3 m Ah/g增加至376.4 m Ah/g,相对变化不大,50次充放电循环后的放电容量保持率从62.6%提高到81.1%(AB3/5%双希夫碱电极)。经过表面处理后的合金电极,腐蚀电位Ec从-0.902 V增至-0.853 V,交换电流密度I0从53.8 m A/g增至142.5 m A/g,极限电流密度IL从511.6 m A/g增至872.8 m A/g,交流阻抗图显示电极与电解液间的电荷转移阻抗减小。结论添加了双希夫碱的合金,循环稳定性、腐蚀电位等综合电化学性能有了较大改善。合金添加双希夫碱后,对强碱电解液的抗腐蚀能力有所增强,这是一种行之有效的合金表面处理方法。     

镀镍石墨粉的电化学性质

利用化学镀方法在石墨粉表面镀覆了一层均匀、完整的金属镍,研究了镀镍石墨粉电极及镀镍石墨粉作为ＭＨ／Ｎｉ电池镍电极导电剂时的电化学性质。实验表明,石墨粉表面镀覆金属镍可增另其电化学活性;用镀镍石墨粉作为电极导电剂时,可以改善镍电极的导电性能,降低电池内阻,提高正极活性物质的利用率,且电池的循环稳定性好,以１Ｃ倍率充放电循环１２０就衰减。     

CuxBy表面修饰对Mg50Ni50合金循环稳定性的影响

用机械合金化法合成了CuxBy合金和非晶态Mg50Ni50储氢合金.用同样的方法以CuxBy对非晶态Mg50Ni50合金进行表面修饰.探索了不同组成的CuxBy合金、同一组成不同比例(质量比,下同)的修饰对Mg50Ni50合金电极循环稳定性的影响.结果表明:不同组成的CuxBy合金对Mg50Ni50合金的表面修饰,都不同程度地提高了Mg50Ni50合金电极的循环稳定性.同一组成不同比例的修饰,对Mg50Ni50合金电极循环稳定性改性效果差异较大.当Mg50Ni50:Cu0..9B0.1=5:1时,初始放电容量为465 mAh·g-1,第50个循环放电容量为222 mAh·g-1.在保持高放电容量的前提下,有效地提高了非晶态Mg50Ni50合金电极的循环稳定性.     

贮氢电极合金电化学容量的评价方法

设计了三种电化学测试系统并进行金属氢化物电极电化学性能对比分析，结果表明，开口式三电极系统测出的放电容量明显高于夹片式和模拟电池系统所测出的放电容量，夹片式电极系统测试的结果和模拟电池系统测试的结果比较一致。     

Surface behavior of pasted nickel electrodes with electrodeposited Co-Ce on substrate

1 Introduction MH/Ni batteries have supper specific energy density, better performance of charging and discharging, and are friendly to the surroundings. So, MH/Ni batteries have been applied widely in power tools[1]. The design of MH/Ni batteries is limi…     

氧化物添加剂对Ni／MH动力电池低温高倍率放电性能的影响

研究了不同氧化物添加剂（CoO,CuO,LazO3,和Y2O3）在高倍率和低温放电条件下对负极性能的影响及机理。实验主要测试的性能有低温放电容量,高倍率（1C,3C,5C和10C）放电容量、充放电电压平台、循环寿命、循环伏安特性和交流阻抗谱,并且分别用SEM、EDS分析了极片的表面形貌和成分。     

石墨烯对La_(0.94)Mg_(0.06)Ni_(3.49)Co_(0.73)Mn_(0.12)Al_(0.20)储氢合金电化学性能的影响

为了提高La_(0.94)Mg_(0.06)Ni_(3.49)Co_(0.73)Mn_(0.12)Al_(0.20)储氢合金的电化学性能,利用石墨烯与储氢合金研磨混合来对其进行表面改性处理。采用X射线粉末衍射仪(XRD)和扫描电子显微镜(SEM)分析合金的相结构和表面形貌。结果表明:添加石墨烯后合金的相结构并没有发生改变,石墨烯包覆在了合金的表面,增大了合金的比表面积,提高了合金的电化学性能。当添加质量分数为5%的石墨烯时,电极的最大放电容量可达到380.6mAh/g,容量保持率S50从69.5%提高到71.1%。添加石墨烯后,交换电流密度、极限电流密度和腐蚀电位均变大、电化学反应阻抗降低,说明电极的动力学性能得到改善。     

Effects of surface modification on the electrode behavior of ball-milled La2Mg17 + 200 wt% Ni composite in alkaline solution

The ball-milled La₂Mg₁₇ + 200 wt% Ni composite is modified with graphite, aluminum, cobalt, titanium and nickel (weight ratio: 5 wt%) by ball-milling for 90 min. The microstructures of the obtained materials were examined by X-ray diffraction and SEM. The electrochemical properties of the obtained materials were measured and compared with those of the original ball-milled composite. It was found that the maximum discharge capacity and high-rate dischargeability of the composites after surface modification by graphite, Co and Ni increased to some extent due to the electrocatalytic activity of the coating element and the decrease of electrochemical reaction resistance on the alloy surface, but the effect of Al and Ti was just on the contrary. On the other hand, the cycling stability of the composites modified with Al, Ti and Ni all improved, and the modification with Ti was the most effective in improving the cycle life. But the modification with graphite, Co led to the worsening of the cycling stability to different degree, especially the modification with graphite.     

The effects of the particle size and active materials on the discharge properties of the Li/Fe(X)S<Subscript>2</Subscript> electrode

Although Li/S batteries produce an efficient initial discharge capacity, they have poor cycle characteristics due to the loss of the active material that occurs in these batteries. Therefore, the material of the metal sulfide series has recently been studied as a substitute. In the present study, the possibility of fine FeS₂ and Fe(x)S₂ compound powders (x=Ni, Co, Mo) are examined using a mechanical alloying method, and the discharge capacity is measured. The mean particle size of the FeS₂ compound powders was measured to be 600 nm at a milling time of 40 h. This data was attained through the utilization of the SEM morphologies. The initial discharge capacity of a Li/FeS₂ battery was 430 mAh/g-FeS₂ if into a fine powder for 20 h milled, and 890 mA/g-FeS₂ if into a fine powder for 30 h milled. Moreover, it was found that if there is an addition of Ni or Co into the compound, it would increase the discharge properties. Fe(x)S₂ composite powders were synthesized in order to improve the cycle life of the battery. From the charge-discharge test results, the initial discharge capacity of the Fe(Ni)S₂ electrode was 845 mAh/g. The initial discharge capacity of the Fe(Co)S₂ electrode was 500 mAh/g, but it showed a better cycle performance than the discharge capacity of electrodes with either additions of Ni or Mo.     

LiMgxNi0.5-xMn1.5O4的制备和电化学性能

为改善LiNi0.5Mn1.5O4的电化学性能,采用流变相法合成掺镁的锂离子电池正极材料LiMgxNi0.5-xMn1.5O4(x=0,0.05,0.1)。XRD测试结果表明所得材料仍为尖晶石结构。电化学性能测试结果显示:当x取值0.1,在3.5～4.9V电压范围内进行充放电循环时,材料LiMg0.1Ni0.4Mn1.5O4具有较好的循环性能,1C充放电时,初始放电比容量可达110.22mAh/g,30次循环后容量衰减率仅为7.7%。     

Effects of modification on performance of natural graphite coated by SiO2 for anode of lithium ion batteries

A stable silicon dioxide film was coated on the surface of natural graphite anode by sol-gel method with Si（OCH2CH3）4, and effects of modification on performance of natural graphite were investigated. The structure and properties of graphite samples were determined by X-ray diffi＇actometry（XRD）, scanning electron microscopy（SEM）, energy-dispersive X-ray spectroscopy（EDS） and electrochemical measurements. The modified graphite shows mainly the layer structure, and silicon dioxide film is amorphous. Compared with the pure natural graphite, the modified graphite exhibits the higher specific capacity of 366 mA-h/g. After 40 charge-discharge cycles, the capacity retention ratio of the modified graphite reaches 99.55%, while that of natural graphite is only 83.04%. The results indicate that the surface modification of natural graphite by SiO2 is effective for improving the electrochemical performance of the natural graphite anode for lithium ion batteries.     

硅电极电火花表面改性的研究

以工业纯硅为电极,通过电火花放电对试样进行表面改性处理.电火花设备型号为EDM7125,工作液为普通煤油,电极材料含硅99.6%,工件材料为45钢和球铁.采用扫描电镜及金相显微镜对试样表面形态进行了研究,对试样表面进行了能谱分析,对试样进行了耐蚀及表层结合强度等试验.结果表明:试样加工后表面形成一层含硅超过16%的合金层.电火花加工球铁石墨基本未脱落,但石墨周围易产生或扩展显微裂纹.高硅层结合强度非常高,进行永久变形时,无剥离和裂纹产生.而且,经电火花加工过的试样耐蚀性得到极大提高.另外,电火花加工,当参数合理时,可达到粉末混入加工的目的,试样可获得好的表面质量.