Ni-MH电池稀土AB_2型贮氢合金负极材料的研究

本文主要对稀土AB_2型贮氢合金用于Ni-MH电池负极材料的电化学性能进行了研究。结果表明，（一）通过优化合金组分，发现多相结构的 LaNi_(2-x)Al_x合金(0.15 ≤ x ≤ 0.25)显示突出的放电性能和长的循环寿命；（二）非化学计量比贮氢合金呈现更高的放电容量和满意的活化性能；（三）原材料的纯度对合金的电极性能影响甚微；（四）退火使合金的结构重整，但对合金电极的电化学性能不利；（五）长时间球磨可以促进活化，但导致电化学容量迅速衰减；短时间球磨大大增加放电容量和提高倍率放电性能；（六）合金电极高能辐照可以激活合金电极的表面活性，促进活化，有效的控制自放电；（七）随着在热碱液中浸泡时间的增加，合金电极的充放电性能得到明显的改善；（八）以镍粉为导电剂的合金电极比以铜粉为导电剂的合金电极有较好的综合电化学性能；（九）温度对合金的电极性能有很大影响。在30 ℃和40 ℃ 测试温度下所得的放电容量几乎相同，但在60 ℃和70 ℃放电容量开始减少。随着温度增加，电极的活化过程加速，高倍率放电能力略有所增加。合金电极呈现不理想的低温放电性能；（十）循环后合金电极的 XPS、XRD、ICP、SEM的图谱分析表明，LaNi_2基合金的腐蚀是造成容量衰减的主要原因，合金的本征衰退也可能是造成容量衰减的原因之一。

Crystal structure and electrochemical properties of rare earth non-stoichiometric AB(5)-type alloy as negative electrode material in Ni-MH battery

The La0.85MgxNi4.5Co0.35Al0.15 (0.05less than or equal toxless than or equal to0.35) system compounds have been prepared by are melting method under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes. The electrochemical properties of these alloys have been studied through the charge-discharge recycle testing at different temperatures and discharge currents. It is found that the La0.85Mg0.25Ni4.5Co0.35Al0.(15) alloy electrode is capable of performing high-rate discharge. Moreover, it has very excellent electrochemical properties as negative electrode materials in Ni-MH battery at low temperature, even at -40degreesC.

Electrode surface modifications improve cathode hydrogen production and anode capacity in Ni-MH batteries

This paper reports results from electrochemical evaluations of electrodes used as cathodes for a hydrogen evolution reaction and anodes in Ni-MH batteries that had been surface-modified by micro-encapsulation, co-deposition and sol-gel methods. The surface modifications produced actual improvements in the corresponding electrochemical reactions by enhancing the performance and/or the mechanical stability of the electrode material. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

MH-Ni电池负极材料

本文报告了MH-Ni电池的进展和存在的问题以及MH-Ni电池负极材料的研究现状,介绍了低温负极材料的进展,并提出了合成低温负极材料要考虑的三个经验原则及第三代储氢合金原则及第三代储氢合金应用于负极材料的前景.

贮氢合金和氟化处理贮氢合金的MH-Ni电池

介绍了贮氢合金材料的种类,同时叙述了经过氟化处理的贮氢合金具有吸氢量大,吸氢速度快,抗毒性强,对气体有选择性和抗微粉化等性能.由氟化处理贮氢合金制成的MH-Ni电池,经过1000次放电循环后,容量仍保持初期的90%.

Effect of mechanical coating with Ni and Ni-5% Al on the structure and electrochemical properties of the Mg-50% Ni alloy

The Mg-Ni metastable alloys (with amorphous or nanocrystalline structures) are promising candidates for anode application in nickel-metal hydride rechargeable batteries due to its large hydrogen absorbing capacity, low weight, availability, and relative low price. In spite of these interesting features, improvement on the cycle life performance must be achieved to allow its application in commercial products. In the present paper, the effect of mechanical coating of a Mg-50 at.% Ni alloy with Ni and Ni-5 at.% Al on the structure, powder morphology, and electrochemical properties is investigated. The coating additives, Mg-Ni alloy and resulting nanocomposites (i.e., Mg-Ni alloy + additive) were investigated by means of X-ray diffraction and scanning electron microscopy. The Mg-Ni alloy and nanocomposites were submitted to galvanostatic cycles of charge and discharge to evaluate their electrode performances. The mechanical coating with Ni and Ni-5% Al increased the maximum discharge capacity of the Mg-Ni alloy from of 221 to 257 and 273 mA h g(-1), respectively. Improvement on the cycle life performance was also achieved by mechanical coating.

Structural and electrochemical characteristics of Mg((55-x))Ti(x)Ni((45-y))Pt(y) metal hydride electrodes

In recent years, Mg-Ni-based metastable alloys have been attracting attention due to their large hydrogen sorption capacities, low weight, low cost, and high availability. Despite the large discharge capacity and high activity of these alloys, the accelerated degradation of the discharge capacity after only few cycles of charge and discharge is the main shortcoming against their commercial use in batteries. The addition of alloying elements showed to be an effective way of improving the electrode performance of Mg-Ni-based alloys. In the present work, the effect of Ti and Pt alloying elements on the structure and electrode performance of a binary Mg-Ni alloy was investigated. The XRD and HRTEM revealed that all the investigated alloy compositions had multi-phase nanostructures, with crystallite size in the range of 6 nm. Moreover, the investigated alloying elements demonstrated remarkable improvements of both maximum discharge capacity and cycling life. Simultaneous addition of Ti and Pd demonstrated a synergetic effect on the electrochemical properties of the alloy electrodes. Among the investigated alloys, the best electrochemical performance was obtained for the Mg(51)Ti(4)Ni(43)Pt(2) composition (in at.%), which achieved 448 mAh g(-1) of maximum discharge capacity and retained almost 66% of this capacity after 10 cycles. In contrast, the binary Mg(55)Ni(45) alloy achieved only 248 mAh g(-1) and retained 11% of this capacity after 10 cycles. (C) 2010 Elsevier By. All rights reserved.

Electrochemical investigation of single-walled carbon nanotubes for hydrogen storage

Electrodes made of purified and open single walled carbon nanotubes behave like metal hydride electrodes in Ni-MH batteries, showing high electrochemical reversible charging capacity up to 800 mAh g(-1) corresponding to a hydrogen storage capacity of 2.9 wt% compared to known AB(5), AB(2) metal hydride electrodes. (C) 2000 Elsevier Science Ltd. All rights reserved.

橄榄石LiFePO_4第一性原理计算研究进展

锂离子电池是一种新型能源,与现有的可充电电池（铅酸电池、镉镍电池和金属氢化物镍电池）相比,在比能量上占有明显优势,目前比能量可高达170～180Wh/kg,是Cd-Ni电池的4倍，MH-Ni电池的2倍。锂离子电池的高T作电压（3．6V）使其相当于3节镉镍电池或金属氢化物镍电池的串连，有利于电池的小型化、轻量化。同时，又具有自放电率低（一般月自放电率小于6％）、长循环寿命的优点.，而且对环境友善，没有污染，是一种绿色能源。自从锂离子电池1991年成功进入世界市场，凭借以上优越性能，在手提电话，摄像机，笔记本电脑和各种便携设备方面的应用越来越广泛。随着新能源的不断开发和利用，对电解液和电极材料的要求也越来越高，特别是对环境的关注和对能源短缺的思考使得人们对锂离子电池进行了新的改进。开发新型电池正极材料是锂离子电池研究的一项重要内容，目前的研究处在实验阶段。由于候选材料的多样性，导致实验上消耗大量的人力、物力和财力，于是从理论上寻求一种计算方法对实验结果进行解释，对相关的材料进行稳定性和电化学性能预测，从而找出一些普遍性规律，已引起研究人员的广泛关注。Ceder于1998年在Nature杂志上发表了《使用第一性原理计算来指导锂离子电池正极材料合成》的研究论文，文中计算出LiAIO_2的嵌入电压高达5．4 V，但纯的LiAIO_2 是电子绝缘体，所以考虑用A1部分替代LiCoO_2 中的Co元素，可以调节电压值，还有利于提高质量比容量。从那时起，理论计算预测锂离子电池正极材料的性能越来越重要。

The design and verification of FPGA CAD toolset

This paper introduces a complete CAD toolset for the implementation of digital logic in a Field-Programmable Gate Array (FPGA) platform. Compared with existing academic toolsets, this toolset introduces formal verification in each step of the tool flow, especially the formal verification of the configuration bitstream. The FPGA CAD tool verification flow using Formality is presented in detail. Using plug-in technology, we have developed an integrated FPGA design kit to incorporate all tools together.

Packing LUT clusters with network flow programming

This paper describes a two-step packing algorithm for LUT clusters of which the LUT input multipliers are depopulated. In the first step, a greedy algorithm is used to search for BLE locations and cluster inputs. If the greedy algorithm fails, the second step with network flow programming algorithm is employed. Numerical results illustrate that our two-step packing algorithm obtains better packing density than one-step greedy packing algorithm.

镍-金属氢化物电池新型负极材料研究

贮氢合金是镍一金属氢化物电池的核心材料，其综合性能的改善是提高镍一金属氢化物电池性能的关键。本研究以探索镍一金属氢化物电池新型负极材料为目的，以非ABS型贮氢合金为研究对象，采用X射线衍射、Rietveld分析、恒电流充／放电、P-C-T曲线及线性微极化等方法，从基础和潜在应用等方面详细研究了非ABS型合金的结构与电化学性能。对La-Ni体系中非ABS型二元合金的结构和电化学性能的研究表明，LaNi_(228)具有最优异的高倍率充电性能；La_2Ni_7合金电极的高倍率放电性能最佳；La_7Ni_3在低温条件下表现出较好的放电性能。然而，所有得到的La-Ni合金电极容量远低于其理论容量。因此，必须通过进一步研究，如元素取代、热处理、表面处理等来提高其电化学容量。对RENi_3（RE＝La，Ce，Pr，Nd，Sm，Gd，Th，Dy，Ho，Er，Y）研究表明：YNi_3合金因其具有最大的晶胞体积，最小的密度，而表现出最好的高倍率充／放电性能及低温放电性能，但其高温放电性能需要进一步提高，以满足实际应用的要求。用Al、Mn、Ti、Fe、Sn、Si、Cr、M。、Cu和Co十种元素取代Ni进行了大量的配方筛选工作。得到了大量的实验数据，并发现LaNi_(3.7)Al_(0.3)合金电极电化学放电容量最高，达290.8mAh／g；LaNi_(3.7)Mo_(0.3)合金电极的高倍率放电性能最好，在以4200mA/g的电流密度下进行放电时，其放电容量仍达到145.8mA/g；而I镍一金属氢化物电池新型负极材料研究镍一金属氢化物电池新型负极材料的研究Al的取代会使合金电极性能对温度不敏感。以我们的实验为基础，进一步进行合金配方的微调，具有可能开发出具有实用价值的贮氢合金的潜力。在Ar保护下用真空电弧炉熔炼合成了四种Lal一xMg：（NICoAI）3．6体系贮氢合金，制成姐卜Ni电池负极，通过恒电流充／放电方法研究了其电化学性能。结果表明：Lal一xMg：（NiCoAI）3．6体系金属氢化物电极较容易活化，室温下具有优异的高倍率放电性能，在以4200mA／g电流放电时，La卜汉gx（NICoAI）36合金电极的放电容量是ABS型合金电极的3倍，达152hah／g，显示出良好的动力学特性。R，入1兮Ni（R：raree田劝，Ca，Y）型合金因能吸引／释放1．8一1．87％质量的HZ而被认为是种很有希望的贮氢合金。但其吸／放氢平台过高，循环寿命短。如何提高Rh厦g剑19循环稳定性是这类合金能否成功商业化的关键。研究发现，Co能够显著提高ABS型合金电极的循环寿命，但其价格太贵。人们发现Al在提高电极寿命方面与C。有类似的作用，但Al元素的添加因其在碱性电解质的作用下在电极表面易生成致密的氧化膜而不利于氢的扩散，进而对高倍率放电性能不利。入物在提高电极表面活性，改善其高倍率放电性方面作用明显。本工作在前面的基础上用Al和MO联合取代Ni，以期待同时改善La一Mg一Ni一Co合金的循环稳定性和高倍率放电性能。详细研究了La07Mg03Ni切一（A105Mo05）x（x：o，0．2，0．4，0．6，0．8）系列贮氢合金的晶体结构和电化学性能。X射线衍射及Rietveld分析发现：所有La07Mg03Ni4D一x（A105Mo05）x合金均为包含PuNi3结构的六方LaZMgNig相、CaCus结构的LaNis主相及L匆Ni7，LaN儿和LaNi杂相的多相结构。合金中La（La，Mg）剑19相及LaNis相的晶格参数及晶胞体积均随合金中Al和Mo含量的增加而增大。用电化学方法测得的RC一T曲线显示：Al和'fo部分取代Ni降低了氢的平台压力。随合金中Al和Mo含量的增加，电极的电化学容量从329．7（x＝0）、徽橇毓孺鑫盆一11瀚加至365．物A吨（＝0．6）后又降低到351．3毗吨（x＝0．8）。当以1200m刀g的电流密度进行放电时，其I｛RD从62．0％沁0）增加到82．1％沁0．8）。线性微极化结果显示：Al和Mo的添加增大了合金表面的交换电流密度，因而也改善了合金电极的高倍率放电性能。另外，Al和M。取代合金中的Ni增大了氢在电极合金中的扩散系数（D），改善了La07Mgo3Ni4。一x（Alo5M。。5）x（X＝o，0．2，0．4，0．6，0．8）合金电极的低温放电性能（LTD）。

镍氢电池复合贮氢合金负极材料的研究进展

根据复合贮氢合金的母体类型即AB5型稀土合金、AB2型Laves相合金、A2B或AB型Mg系合金、V基bcc固溶体型合金和La-Mg-Ni系新型合金,将Ni/MH电池复合贮氢合金负极材料分为相应的5种类型;综述了此类材料的制备方法、微观结构与电化学性能、分析表征方法及机制研究等,提出了目前研究中存在的问题与不足,并对该类材料的研究发展做了展望。

Effect of substitution of chromium for nickel on structure and electrochemical characteristic of Ti0.26Zr0.07V0.24Mn0.1Ni0.33 multi-phase hydrogen storage alloy

Ti-Zr-V-Mn-Ni-based multi-component alloys demonstrate high discharge capacity in KOH electrolyte. However, the drastic decrease in their discharge capacities makes them unsuitable for use as negative electrode material in the Ni/MH battery. In present work, Ni is partially replaced by Cr in the Ti-Zr-V-Mn-Ni-based alloys to improve their cycle life. The effects of Cr substitution on microstructures and the electrochemical characteristics of the alloys are investigated. It is found that Cr substitution is very effective to improve the cyclic durability of the alloys although the discharge capacity decreases with changing x from 0.05 to 0.20. Some kinetic performances have been also investigated using electrochemical impedance spectroscopy (EIS) and potentiostatic discharge technique.