镍硫钴析氢电极的制备及性能研究

采用电沉积方法制备Ni-S-Co合金电极,通过正交实验和极化曲线测试研究了CoSO4·7H2O浓度、电流密度、电镀液温度、电沉积时间和电解液温度对Ni-S-Co电极析氢性能的影响.采用SEM,XRD和EDXA对镀层的形貌、结构和组成进行观察和分析.实验结果表明:制备具有最佳析氢活性的Ni-S-Co电极的工艺条件是25 ...     

Ni对非晶态Co-B合金电化学储氢性能的影响

通过化学还原共沉积法引入元素Ni制备了三元非晶态Co-Ni-B合金,并研究了元素Ni对非晶Co-B合金电化学储氢性能的影响。结果表明,含镍23.8at%非晶态Ni-Co-B合金的可逆放电容量约为250mAh/g,较非晶Co-B合金下降约20mAh/g,但循环稳定性二者相同,即在650mA/g的高电流密度下循环60次容量几乎保持不变。但进一步增加Ni含量,含镍35.8at%的非晶态Ni-Co-B合金的放电容量和循环稳定性都较不掺杂时发生大幅下降。但是,元素Ni的引入能有效抑制高电流密度充电过程中Co-B合金表面大量氢气的析出,减小电极放电电压平台和容量在循环过程中的波动。这可能得益于以下2个原因:(1)非晶Ni-Co-B合金对水分解的电催化活性降低;(2)吸附态氢原子在非晶Ni-Co-B合金基体中的扩散速度高于在Co-B合金中的扩散速度。     

钛基镍钴合金电极的制备及析氢性能

目的降低电极的析氢过电位,提高析氢性能,从而降低电解水制氢的成本,促进氢储能技术的发展。方法通过异相共沉积法,制备了镍钴合金电极。利用场发射扫描电镜(SEM)、电化学交流阻抗(EIS)对纯镍电极及镍钴合金电极进行表征,采用阴极极化曲线(LSV)探究了电沉积液中Ni/Co元素的比例、电沉积电位及电沉积时间对镍钴合金电极析氢性能的影响。结果 SEM结果揭示了纯镍电极及镍钴合金电极表面分别是粒径约为100 nm左右的镍颗粒和镍钴颗粒。EIS结果说明了镍钴合金电极的导电性能优于纯镍电极。此外,纯镍电极、镍钴合金电极的阴极极化曲线测试表明在电流密度为30 mA/cm~2时,镍钴合金电极的析氢过电位比纯镍电极降低55 mV,降低了近20%。结论通过异相共沉积法制备镍钴合金电极,制备方法简单、方便、快速,其析氢性能优于纯镍电极。镍钴合金电极的最优制备工艺条件为:NiSO_4·6H_2O 27 g/L,CoSO_4·7H_2O_3 g/L,H_3BO_3 10 g/L,Na_2SO_4 10 g/L,柠檬酸10 g/L,十二烷基硫酸钠0.1 g/L,pH值4.0,电沉积电位-1.3 V,电沉积时间10 s。     

热声耦合法制备氟化镁钠膜机制及其生物腐蚀性能

采用热声耦合法在Mg-Gd-Zn-Zr镁合金表面制备氟化镁钠膜,用点滴法、电化学法和析氢腐蚀法评定其耐蚀性,用扫描电子显微镜（SEM）及能谱仪（EDS）分析氟化镁钠膜表面形貌及成分。结果表明,热声耦合法制备的氟化镁钠颗粒尺寸细小;氟化镁钠膜的变色时间随工艺时间延长而增大;氟化镁钠膜显著提高镁合金在模拟体液（SBF）中的容抗弧半径和阻抗值,降低其腐蚀电流密度和析氢速率;氟化镁钠膜具有促进钙磷沉积作用,其降解形成的新氟化物 磷酸盐膜具有进一步保护镁合金基体作用。     

镁海水电池阳极活化机理研究

研制了新型Mg-Hg-X合金阳极材料,用扫描电镜(SEM)、能谱、X-射线衍射(XRD)和电化学测试等方法分析了镁合金阳极材料在海水介质中腐蚀前后的微观结构、表面形貌及表面元素的组成,研究了Mg-Hg-X合金阳极的溶解过程及活化机理.结果表明:在放电初期,Mg-Hg-X合金阳极材料中的第2相粒子随点腐蚀的发生直接脱落,形成腐蚀坑,随后Mg-Hg-X合金阳极溶解在介质中的合金元素离子与基体镁发生反应,再沉积于镁阳极材料表面的点蚀孔中,形成Hg、X的沉积层,破坏钝化膜的结构,降低了Mg-Hg-X合金阳极极化.使电极电位负移,同时沉积的具有高析氢过电位的Hg、X抑制了析氢腐蚀.     

A new method to improve surface morphology of Ni-Fe-Mo-Co alloy electrode and its catalytic activity for HER

A new pretreatment method has been developed to improve the catalytic activity of the Ni-Fe-Mo-Co alloy elec- trode for hydrogen evolution reaction (HER). The procedure involves pre-electrolyzing the Ni-Fe-Mo-Co alloy electrode in 30% KOH solution containing 10% potassium sodium tartrate at 70°C for 2 h, until some of the Mo and Fe elements are leached out. The surface morphology of the Ni-Fe-Mo-Co alloy demonstrates a unique hive-like structure after the pre- treatment, which has the pore size in a nanometer range (about 50 nm), a very large real surface area, and good stability. The results of the electrochemical studies show that compared to other similar electrode materials and the treated Ni-Fe-Mo-Co electrode by leaching method, the pre-treated Ni-Fe-Mo-Co electrode has a much lower overpotential and much higher exchange current density for HER. In addition, a long-term continuous electrolysis test with a current interrup- tion shows that the Ni-Fe-Mo-Co alloy has excellent catalytic stability.     

Damage Behavior of SnAgCu Solder under Thermal Cycling

电子封装焊点的热循环失效是焊点材料损伤逐步发展的结果,本工作旨在对SnAgCu钎料的热循环损伤失效行为进行研究.以连续损伤力学理论为基础,提出了一种适用于热循环条件下SnAgCu钎料蠕变-疲劳交互作用的损伤模型.据此,设计了热力循环实验和热循环实验用以标定损伤模型相关参量.自行设计了双金属剪切加载装置并结合温度循环实验,对SnAgCu钎料的热力耦合损伤行为进行了深入研究.以电阻变化率作为损伤变量,并在热循环的不同周次测量试样的损伤值从而验证损伤模型.结果表明:所提出的幂函数形式的损伤模型能较好的描述SnAgCu钎料的热循环损伤演变.最后,对热循环条件下SnAgCu钎料试样的微观组织演变进行了SEM分析,从而揭示其损伤演变机理.     

Influence of Nd on Microstructure and Bio-corrosion Rsistance of Mg-Zn-Mn-Ca Alloy

将0.4%(质量分数,下同)的Nd添加到Mg-6Zn-1Mn-0.5Ca合金中,以研究稀土元素Nd对合金显微组织和耐生物腐蚀性能的影响。采用金相(OM)、带能谱的扫描电镜(SEM+EDS)以及XRD等手段分析了合金的微观组织。采用静态浸泡、析氢和电化学极化等手段研究了合金在模拟体液(SBF)中的耐腐蚀性能。结果表明,随着Nd的添加,合金的显微组织得到了明显的细化。在Mg-6Zn-1Mn-0.5Ca-0.4Nd合金中形成了2种第二相的机械混合物Ca2Mg6Zn3+Mg41Nd5。在SBF中浸泡7d以后,较多的此种混合物仍残留于含Nd合金的表面,而在不含Nd的合金中,只有极少量的颗粒状Ca2Mg6Zn3残留在其表面。故Nd的添加显著提高了Mg-6Zn-1Mn-0.5Ca合金的耐生物腐蚀性能。     

负极集流体表面处理方法及对电池性能的影响

在高能扣式碱性锌锰电池负极集流体表面制备出一种性能良好的高氢过电位材料Zn-In合金.采用线性扫描阴极极化曲线、X射线衍射(XRD)、扫描电镜(SEM)、能谱分析(EDS)、交流阻抗(EIS)及电池气胀高度检测等方法研究Zn-In合金材料的性质、各组分的含量以及对电池性能的影响.结果表明:该Zn-In合金材料显著提高了集流体析氢过电位,从而有效地抑制电池气胀, 改善电池性能,同时降低生产成本,且对环境友好,因此用于代替In电沉积具有广阔的应用前景.     

Effects of Adding Cerium to Lithium on Properties of Lithium Anode

研究了在 30 ℃的 LiOH 碱性水溶液中,添加合金元素 Ce 对锂负极性能的影响。开路电位下的自腐蚀析氢速率及电化学测试结果表明,添加 Ce 对锂负极的析氢速率有明显的抑制作用。Ce 添加量为 0.08%(质量分数)时,对锂负极的缓蚀效率接近 83.3%。SEM观察表明,与纯锂负极相比,Li-Ce 合金负极放电后的表面膜更加致密少孔。XRD 分析表明,该表面膜里除了含有 LiOH 及 LiOH·H2O外,还有 Ce(OH)3存在,说明在碱性 LiOH 水溶液电解质中,Li-Ce 合金负极表面形成的 Ce(OH)3沉淀物在抑制自腐蚀析氢及影响放电电位方面起着关键作用。     

Al-Mn中间合金对Mg-Al-Pb-Mn合金组织和电化学性能的影响(英文)

Mg-Al-Pb合金是一种新开发的海水激活电池材料。采用熔炼浇注法制备Mg-6Al-5Pb-0.5Mn系列合金和Mg-6Al-5Pb合金。其中,Mg-6Al-5Pb-0.5Mn系列合金是以Al-15%Mn、Al-30%Mn和Al-50%Mn中间合金为添加剂制备的。采用金相显微镜和扫描电子显微镜表征其组织,采用电化学方法、析氢法和失重法研究其性能。结果表明:以Al-50%Mn中间合金为添加剂制备的Mg-6Al-5Pb-0.5Mn合金具有最负的放电电位(-1.66 V),最小的腐蚀电流密度(7μm/cm2)和自腐蚀速率(0.51 mg·h-1·cm-2)。这可能是因为Al11Mn4相的存在,不仅有利于腐蚀产物的脱落和增大电化学反应面积,而且也提高电化学活性。     

DEGRADATION BEHAVIORS OF NEW TYPE TiV-BASED HYDROGEN STORAGE ELECTRODE ALLOYS

The degradation behaviors of the TiV-based multiphase hydrogen storage alloy Ti0.8,Zr0.2V3.2Mn0.64 Cr0.96Ni1.2 during electrochemical cycling in alkaline electrolyte have been studied by XRD, SEM, EIS and AES measurements. XRD analysis indicates that the alloy consists of a C14-type Laves phase and a V-based solid solution. The lattice parameters of both phases are increased after discharged with cycling, which indicates that more irreversible hydrogen remains not discharged in the alloy. It should be responsible for the decrease of discharge capacity. SEM micrographs show that after 10 electrochemical cycles, a large number of cracks can be observed in the alloy, existing mainly in the V-based solid solution phase. Moreover, after 30 cycles, the alloy particles are obviously pulverized due to the larger expansion and shrinkage of cell volumes during hydrogen absorption and desorption, which induces the fast degradation of the TiV-based hydrogen storage alloys. EIS and AES measurements indicate that some passive oxide film has been formed on the surface of alloy electrode, which has higher charge-transfer resistance, lower hydrogen diffusivity, and less electro-catalytic activity. Therefore it can be concluded that the pulverization and oxidation of the alloy are the main factors responsible for the fast degradation of the TiV-based hydrogen storage alloys.     

Surface analysis, hydrogen adsorption and electrochemical performance of alkali-reduce treated hydrogen storage alloy

The hydrogen storage alloy powders (M1Ni4.0Co0.6Al0.4, M1 = rich-La mischmetal) were treated in a hot 6 mol/L KOH 0.02 mol/L KBH4 solution, the surface compositions and chemical states of the treated and untreated alloys were analyzed by XPS and EDX, the hydrogen adsorption on the surface of these alloys was evaluated by thermal desorption spectroscopy (TDS), the effects of the surface treatment on the electrochemical performances of the alloy electrodes were investigated. The results show that the hydrogen adsorption is greatly strengthened by the surface modification, and hence leads to marked improvement in the electrocatalytic activity, the treated alloy exhibits higher exchange current density and lower apparent activation energy for the hydrogen electrode reaction than the untreated alloy.     

恒压电沉积 Pt-Ni 合金催化剂的形貌控制及其对催化剂性能的影响

目的通过对电沉积过程中基体亲水性及电解液温度参数的控制,实现对Pt-Ni催化剂的形貌及催化性能的控制。方法采用恒电压沉积技术制备Pt-Ni合金催化剂。利用5%(质量分数)Nafion对多孔碳布基体表面进行亲水修饰,并控制电解液温度,合成具有不同形貌的Pt-Ni合金催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、能量色散谱(EDS)、循环伏安(CV)、单电池极化性能等测试技术对制备的催化剂进行物理及电化学表征。结果碳布基体表面经适量的Nafion修饰后,电沉积制备的合金催化剂颗粒细小,分布均匀。当碳布基体表面修饰的Nafion含量达到0.8 mg/cm2时,催化剂单电池极化性能最佳。另外,较高电解液温度下制备得到的球状形貌具有更大的电化学活性表面积(ECSA),更高的催化活性,优于较低温下制备的"雪花"状催化剂的性能。其中,50℃下电沉积制备的Pt-Ni合金催化剂ECSA达到47.6 m2/(g Pt),单电池运行过程中最大功率密度达到77.8 m W/cm2,具有最高的催化活性。结论适量Nafion修饰后的亲水多孔碳布基体上电沉积Pt-Ni合金催化剂性能更加优越。电解液温度的控制对恒电压沉积的Pt-Ni合金表面形貌控制有重要意义。     

Corrosion characterization of Mg-8Li alloy in NaCl solution

The corrosion mechanism of Mg-8Li alloy in NaCl solution was investigated by electrochemical testing and SEM observation. The electrochemical results indicated that the corrosion resistance of Mg-8Li alloy in 0.1 M NaCl solution gradually deteriorated with increasing of immersion time expect for 2 h immersion, which was consistent with the SEM observation of corrosion morphology. Mg-8Li alloy exhibited filiform type of attack under significant anodic control of magnesium solution reaction. The cathodic reaction was driven by hydrogen evolution reaction. The presence of filiform corrosion also proved a resistant oxide film naturally formed on the surface of Mg-8Li alloy.     

Electro-deposition of Co–La alloy films in urea melt and their performances

The Co–La alloy film was electro-deposited in urea melt. The co-deposition behavior, the effect of the cathodic current density on the composition and the surface morphology of the coating were examined, respectively. As a result, lanthanum is co-deposited with cobalt to form Co–La alloy under the inducement effect of cobalt. With the increase of the cathodic current density, La content of the deposit rises at first, then decreases, and reaches a maximal value at the current density of 30 mA cm⁻². Meanwhile, the size of the coating particles becomes small. The more content of Co in the deposit is, the more the saturation magnetization is. The crystallization behavior of the coating was studied by using the differential scanning calorimetry and the X-ray diffraction. The as-plated deposit consists of main amorphous phase and a little amount of hexagon cobalt phase (P6₃/mmc). The amorphous phase was converted into Co–La (Fm3m) phase at 438.9 °C, and hexagon cobalt phase was crystallized into cubic cobalt at 687.1 °C. The electro-catalytic activity of the hydrogen evolution for the Co–La alloy was studied by using electrochemical experiments. The results showed that the electro-catalytic activity of the hydrogen evolution of the alloy is better than that of cobalt.     

Ni元素对非晶合金Mg_(65)Cu_(25)Gd_(10)在NaCl溶液中腐蚀行为的影响

采用析氢腐蚀实验比较了非晶合金Mg65Cu25Gd10和Mg65Cu20Ni5Gd10在1%NaCl溶液中腐蚀性能。利用电化学测试技术和场发射扫描电子显微镜(FESEM)对两非晶合金在NaCl溶液中的腐蚀行为进行了研究。析氢腐蚀实验表明,Ni的加入大大提高了非晶合金Mg65Cu25Gd10抗蚀性能,极化曲线测试结果也表明Mg65Cu20Ni5Gd10非晶合金的腐蚀电流远远小于Mg65Cu25Gd10非晶合金。EIS测试表明,电化学阻抗谱测试结果显示Mg65Cu20Ni5Gd10非晶合金电荷转移电阻高于Mg65Cu25Gd10非晶合金。腐蚀产物形貌观察表明,Ni的加入使非晶合金Mg65Cu20Ni5Gd10腐蚀表面膜更为致密。结合各测试结果,探讨了Ni的加入提高镁基非晶合金耐蚀性机理。     

Influence of the cathodic intermetallics distribution on the reproducibility of the electrochemical measurements on AA5083 alloy in NaCl solutions

The corrosion behavior of alloy AA5083 in solutions of NaCl at 3.5% is controlled by the density of the cathodic precipitates of Al(Mn,Fe,Cr) present in the alloy. These precipitates are not distributed homogeneously over the surface of the alloy. Further, their presence conditions the electrochemical response of the alloy. For these reasons, in order to guarantee the reproducibility of electrochemical tests on this alloy, it is necessary to determine the minimum surface area exposed to the medium which represents the average behavior of the system. In the present study, a systematic analysis has been conducted on the degree of reproducibility of electrochemical tests as a function of the area of surface exposed, for the alloy AA5083 in solutions of NaCl at 3.5%. A high dependence between the dispersion of the electrochemical data and the exposed area has been established. This behavior contrast with those of other alloys, like AA1050, which is not conditioned by the values of exposed area. This has been related to the much lower cathodic precipitates density in this alloy.     

稀土氧化物对贮氢合金电极电化学性能的影响

研究了稀土氧化物La_2O3_,CeO_2,Nd_2O_3和Y_2O_3对AB_5型贮氢电极电化学性能的影响。研究表明,除Y2_O3_外,其余的稀土氧化物可提高贮氢电极的1C放电容量和放电电压,延长贮氢电极的循环寿命,且对贮氢电极性能有利的顺序为:La2_O3_>CeO2_>Nd2_O3_;稀土氧化物添加量越多,贮氢电极的循环稳定性越好,但对贮氢电极的1C放电容量和放电电压的影响存在最佳值。造成这些结果的原因是:稀土氧化物增大贮氢合金颗粒间的接触电阻;稀土氧化物的催化作用;稀土氧化物对镍催化剂的稳定作用及抑制贮氢合金进一步氧化的作用。     

Magnesium-based hydrogen storage materials modified by mechanical alloying

The effects of mechanical alloying on microstructure and electrochemical performance of a Mg–Ni–Y–Al hydrogen storage alloy in 6 M KOH solution were studied. The ball-milled powders were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected-area electron diffraction (SED) and energy dispersion spectrometry (EDS). TEM and EDS results clearly reveal that the smaller nickel clusters or particles were well dispersed on the surface of larger magnesium alloy particles by mechanical grinding for 72 h. With an increase in milling time to 240 h, the nickel clusters or particles disappeared and a new monophase alloy with amorphous structure was formed. The electrochemical capacity of the modified material significantly increased with increasing milling time within 72 h and then dropped to nearly nil when the milling time reached 240 h. The capacity decay, however, was always improved with increasing grinding time. Further analysis and discussion were made based on d.c. polarization and a.c. impedance spectroscopy measurement results.