Influence of electroless nickel plating of hydrogen-absorbing alloys on cycle characteristics of nickel-metal hydride batteries

The effects of electroless nickel plating of a hydrogen-absorbing alloy on the cycle characteristics of a nickel-metal hydride battery were investigated. The cycle life was improved by employing an electroless nickel-plated hydrogen-absorbing alloy for the negative electrode, which retained the same high-rate level and low-temperature characteristics compared to a cell using a non-plated hydrogen-absorbing alloy. The electroless nickel-plated hydrogen-absorbing alloy provided better electrochemical characteristics when its surface was partly and tightly covered by nickel particles under optimal electroless plating conditions.     

Suppression mechanism of the self-discharge reaction in nickel-metal hydride batteries using a sulfonated polyolefin separator

The suppression mechanism of the self-discharge reaction in nickel-metal hydride batteries using a sulfonated polyolefin separator was investigated with sealed-type AA size cells. The experimental results indicate that a sulfonated polyolefin separator effectively suppresses the self-discharge reaction in nickel-metal hydride batteries by trapping nitrogen-containing redox shuttle substances. It is also found that a sulfonated polyolefin separator traps the shuttle substances as gaseous ammonia. In the experiment examining the influence of the amount of the shuttle substances on the self-discharge, the starting point of the self-discharge agreed well with the point at which the nitrogen adsorption capacity of a sulfonated polyolefin separator reached its maximum.     

Al含量对AB5型储氢合金电极低温和高倍率性能的影响

系统地研究了Al含量对富Ce储氢合金MmNi_4-xCo_0.7Mn_0.3Al_x（x=0,0.1,0.2,0.3）电极综合电化学性能,尤其是对低温和高倍率性能的影响。在常温下,储氢合金电极放电容量和循环性能均随着Al含量的增加而增加,而高倍率放电性能严重下降。-20℃时,放电容量仍随着Al含量的增加而增加,但在-40℃下放电容量随之严重衰退。电化学动力学结果表明,常温下高Al合金高倍率性能的降低主要是由于电极表面电荷转移过程的恶化;低温-40℃下,Al同时降低了合金电极的表面电催化活性以及体相H扩散能力,严重恶化电极过程动力学,从而导致了高Al合金极低的容量及电压输出。考虑到各电极的综合电化学性能,MmNi_3.8Co_0.7Mn_0.3Al_0.2为最佳的成分配比。     

Al含量对AB5型储氢合金电极低温和高倍率性能的影响

系统地研究了Al含量对富Ce储氢合金MmNi_4-xCo_0.7Mn_0.3Al_x（x=0,0.1,0.2,0.3）电极综合电化学性能,尤其是对低温和高倍率性能的影响。在常温下,储氢合金电极放电容量和循环性能均随着Al含量的增加而增加,而高倍率放电性能严重下降。-20℃时,放电容量仍随着Al含量的增加而增加,但在-40℃下放电容量随之严重衰退。电化学动力学结果表明,常温下高Al合金高倍率性能的降低主要是由于电极表面电荷转移过程的恶化;低温-40℃下,Al同时降低了合金电极的表面电催化活性以及体相H扩散能力,严重恶化电极过程动力学,从而导致了高Al合金极低的容量及电压输出。考虑到各电极的综合电化学性能,MmNi_3.8Co_0.7Mn_0.3Al_0.2为最佳的成分配比。     

Effect of separators on the self-discharge reaction in nickel-metal hydride batteries

The effects of separators on the self-discharge behavior and the suppression of self-discharge by a sulfonated polyolefin separator were investigated with test cells. The experimental results indicate that a sulfonated polyolefin separator effectively suppresses the self-discharge reaction in nickel-metal hydride batteries. It is also found that a sulfonated polyolefin sheet does not necessarily need to be sandwiched by positive and negative electrodes to act as a separator; it can be placed anywhere within a cell to suppress the self-discharge reaction. The self-discharge reaction is considered to be suppressed by trapping redox shuttle substances, especially nitrogen-containing compounds, by the separator.     

利用球磨制备AB2-AB5复合贮氢合金及其电极性能和微观结构研究

为了改善Zr基AB₂-型贮氢合金的电极性能，本文选择稀土基AB₅型贮氢合金作为表面改性剂，将Zr_0.9Ti_0.1(Mn_0.35Ni_0.50V_0.15)₂(简称AB₂)合金与稀土基AB₅型合金(简称AB₅)进行混合和球磨处理，制备了AB₂-AB相似文献   

贮氢合金LaNi_（3．8）Co_（0．5）Mn_（0．4）Al_（0．3）表面

贮氢合金ＬａＮｉ_（３．８）Ｃｏ_（０．５）Ｍｎ_（０．４）Ａｌ_（０．３）表面化学镀镍的研究张允什，陈军（南开大学新能源材料化学研究所，天津，３０００７１）关键词贮氢合金，化学镀镍，镍／氢电池目前，稀土系贮氢合金应用于镍／金属氢化物（镍／氢）电池存在的...     

Performance and scaling of a 1.2 V/1.5 Ah nickel/metal hydride cell to a 6 V/1.5 Ah battery

A 1.2 V/1.5 Ah positive-limited nickel/metal hydride cell has been studied to determine its charge-discharge characteristics at different rates in conjunction with its AC impedance data. The faradaic efficiency of the cell is found to be maximum at ∼70% charge input. The cell has been scaled to a 6 V/1.5 Ah battery. The cycle-life data on the battery suggest that it can sustain a prolonged charge-discharge schedule with little deterioration in its performance. Received: 17 November 1998 / Accepted: 5 February 1999     

Solid-state metal hydride secondary batteries using heteropolyacid hydrate as an electrolyte

In order to enhance the performance of a solid-state MnO₂-metal hydride battery using H₃PMo₁₂O₄₀ · 20H₂O as an electrolyte, a moderate amount of the electrolyte was added to both positive and negative electrodes. The high rate characteristics of the battery were improved significantly by optimizing the electrolyte content in the electrodes; the resulting battery was able to operate over 140 cycles, even at a current density of 20 mA/g alloy, which is large enough for the batteries using inorganic solid electrolytes, and keep the discharge efficiency about 90%. The improvement of battery performance appears to be caused by an increase in electrode-electrolyte interface area. The AC impedance analyses revealed that the resistance of interface is decreased by the addition of a suitable amount of the electrolyte, suggesting an increase in the interface area.     

四元镧镍系吸氢合金的结构与性质

本文通过吸氢测试和XPS等技术，研究了化学法制备的LaNi_5-x-yM_xM_y′型四元吸氢合金的结构、吸放氢性质、表面性质及其相互关系。这些合金有良好的表面性质，易活化，吸氢量较高。在La-Ni-Co-Mn系列中，氢化物稳定性与合金的晶胞体积之间存在近似的直线关系。     

La-H化合物对LaMg2Ni合金中Mg2Ni相吸氢过程的影响

采用感应熔炼技术在Ar气氛保护下制备得到LaMg2Ni与Mg2Ni合金。X射线衍射(XRD)图表明LaMg2Ni合金在吸氢过程中分解为LaH3相和Mg2NiH4相,放氢过程中LaH3相转化为La3H7相。与Mg2Ni合金相比,LaMg2Ni合金显示出优良的吸氢动力学性能,这是由于镧氢化合物的存在及其在吸氢过程中所发生的相转变所造成的。LaMg2Ni合金280 s内吸氢即可达到最大储氢量的90%以上,而Mg2Ni合金则需要1200 s才能达到,且在相同温度下LaMg2Ni合金的吸氢反应速率常数大于Mg2Ni合金速率常数。镧氢化合物不仅有利于改善动力学性能,而且可以提高热力学性能。LaMg2Ni合金中的Mg2Ni相氢化反应焓与熵分别为-53.02 kJ.mol-1和84.96 J.K-1.mol-1(H2),这一数值小于单相Mg2Ni氢化反应焓与熵(-64.50 kJ.mol-1,-123.10 J.K-1.mol-1(H2))。压力-组成-温度(P-C-T)测试结果表明在603 K至523 K温度范围内,LaMg2Ni合金储氢容量保持稳定为1.95wt%左右,然而Mg2Ni合金的储氢容量则由4.09wt%衰减为3.13wt%,Mg2Ni合金的储氢容量在523K低温下仅为603 K时的76.5%,表明镧氢化合物能够改善Mg2Ni合金低温下的吸放氢性能。     

不同碱溶液表面处理对稀土镁镍基储氢合金的影响

采用相同浓度即6 mol·L^-1 LiOH、NaOH和KOH对稀土镁镍基储氢合金进行表面处理,研究了不同碱溶液和不同处理时间对合金表面形貌、组成和电极电化学性能的影响。研究表明,合金经6 mol·L^-1 NaOH溶液处理10 min后具有最好的综合电化学性能。但随着处理时间的延长,采用6 mol·L^-1 NaOH溶液处理的合金放电容量衰减明显,实验证明这是由合金表面稀土元素和Al元素的大量溶解进入碱溶液造成的。3种碱溶液比较,LiOH溶液能有效去除合金表面镁元素减少合金在碱溶液处理过程中的氧化,虽然形成的表面不利于H在合金表面的吸脱附,却能有效提高合金在碱溶液中的抗腐蚀能力,提高合金的循环稳定性。     

The electronic structures of polymeric beryllium hydride and polymeric boron hydride

The band structure of linear polymeric beryllium hydride is here calculated by anab initio technique. The doubly-degenerate valence band has symmetry and is composed of a berylliump orbital and an antisymmetric combination of the appropriate hydrogen 1s orbitals. The Koopmans' ionization potential is calculated to be 16.1 eV and the direct band gap, found atX, is 15.2 eV. The charge distribution shows an electron drift of approximately 0.15 electrons from beryllium to the hydrogen atoms. The total energy calculation indicates that polymeric beryllium hydride is more stable than the monomer while polymeric boron hydride is less stable than the monomeric species. From the polymeric boron hydride system, an alternating-bond model is more stable than a symmetric bond model. The energy band structures of both models reveal that electron delocalization along the polymer chain is weak.     

稀土元素对R-Y-Ni系A2B7型无镁储氢合金微观结构和电化学性能的影响

采用真空电弧熔炼及退火处理制备R-Y-Ni系A_2B_7型R0.3Y0.7Ni3.25Mn0.15Al0.1(R=Y,La,Pr,Ce,Nd,Gd,Sm)储氢合金,系统研究稀土元素R对合金微观组织与结构、储氢和电化学性能的影响。XRD和SEM-EDS分析表明,合金退火组织由Ce2Ni7型主相、PuNi3型及少量Ca Cu5型相组成,Ce2Ni7型主相的晶格常数a、c及晶胞体积V均随稀土R原子半径的减小而依次降低。该合金均具有明显的吸放氢平台,常温下最大吸氢容量为1.17%~1.48%(w/w),吸氢平台压Peq为0.037~0.194 MPa。电化学分析表明,退火合金电极的电化学活化性能优良,R=La合金具有最高的放电容量(389.2 mAh·g-1)和较佳的容量保持率(充放电循环100次后的S100=85.7%),其中合金微观组织的不均匀性及稀土元素的电化学腐蚀是影响电极循环稳定性的主要原因。合金电极的高倍率放电性能(电流密度为900 m A·g-1)HRD900=71.05%~86.94%,其电极反应动力学控制步骤主要由氢原子在合金体相中的扩散速率所控制。     

Y掺杂对氢氧化镍电极高温性能的影响

合成了内掺稀土元素Y的β-Ni(OH)2和α-Ni(OH)2材料, 并通过XRD、TEM、CV 和充放电测试等方法研究了Y元素对这两种晶型活性材料的结构、形貌以及高温电化学性能方面的影响, 发现Y元素可显著提高β-Ni(OH)2和α-Ni(OH)2材料的高温性能, 且作用机理相同, 均是通过提高析氧过电位来改善镍电极的高温充电效率. 但是α-Ni(OH)2在高温下的相稳定性仍有待提高.     

Ml(NiCuAlZn)5储氢合金粉末的包覆处理

镍氢电池;Ml(NiCuAlZn)5储氢合金粉末的包覆处理     

Solid-state metal hydride batteries using ZrO2·nH2O as an electrolyte

ZrO₂·1.5H₂O or ZrO₂·1.5H₂O-KOH composite was used as an electrolyte in order to develop a solid-state nickel-metal hydride battery. The battery using the ZrO₂·1.5H₂O-KOH composite had rechargeability, but had a very low discharge efficiency, even at low current density. However, the performance of the battery was prominently improved by enlarging the electrode-electrolyte interface area. The resultant battery exhibited the remarkably longer cycle life, the higher discharge efficiency, and the lower polarization: it was able to operate over 150 cycles at 10 mA/g alloy.     

MgH2-MoS2-PP复合材料的储氢性能

通过球磨法制备了MgH₂-MoS₂-PP（PP=热解聚苯胺,w_MOS2=w_PP=8.33%）复合材料。与纯MgH₂对比研究发现,复合材料的初始放氢温度从650 K下降到550 K,并且在573 K下,75 min内的放氢量从0.38%（w/w,下同）提高到2.36%。在423 K下,放氢后产物可在40 min内吸氢2.45%,比纯MgH₂高出2.13倍。放氢反应的活化能比纯MgH₂（101.83 kJ·mol^-1）降低了28.81 kJ·mol^-1。MgH₂-MoS₂-PP复合材料的性能提高是由于PP能够均匀地减小Mg颗粒尺寸,并提高MoS₂在体系放氢与再吸氢过程中的催化效率。     

MgH2-MoS2-PP复合材料的储氢性能

通过球磨法制备了MgH₂-MoS₂-PP（PP=热解聚苯胺,w_MoS2=w_PP=8.33%）复合材料。与纯MgH₂对比研究发现,复合材料的初始放氢温度从650 K下降到550 K,并且在573 K下,75 min内的放氢量从0.38%（w/w,下同）提高到2.36%。在423 K下,放氢后产物可在40 min内吸氢2.45%,比纯MgH₂高出2.13倍。放氢反应的活化能比纯MgH₂（101.83 kJ·mol^-1）降低了28.81 kJ·mol^-1。MgH₂-MoS₂-PP复合材料的性能提高是由于PP能够均匀地减小Mg颗粒尺寸,并提高MoS₂在体系放氢与再吸氢过程中的催化效率。     

Synthesis, structure and physical properties of GdCu4Al and GdCu4Ga

Two non-stoichiometric Gd compounds, GdCu_5−xTr_x (Tr=Al, Ga) have been synthesized from the corresponding elements by high temperature reactions in sealed tantalum containers. They crystallize in the hexagonal CaCu₅-type (Pearson's symbol hP6, space group P6/mmm, No. 191) with lattice parameters determined from single-crystal X-ray diffraction at room temperature as follows: a=5.0831(10) Å; c=4.156(2) Å for GdCu_3.98(4)Al_1.02(4), and a=5.1025(10) Å; c=4.155(2) Å for GdCu_3.9(1)Ga_1.1(1), respectively. Structure refinements from single crystal X-ray diffraction data reveal that substitution of Cu for Al or Ga takes place preferably on one of the two transition metal sites with site symmetry mmm (3g). Both compounds order antiferromagnetically below ∼40 K and ∼36 K, respectively, as determined from temperature dependent dc-magnetization, resistivity and heat-capacity measurements.