添加剂对金属陶瓷惰性阳极电解腐蚀的影响

采用粉末冶金法制备了无添加剂和添加V2O5的Ag-NiFe2O4/NiO金属陶瓷惰性阳极.铝电解试验在960 ℃进行,电流密度为0.5 A/cm2,电解时间为8 h,研究了无添加剂和添加2.0%(质量分数,下同)V2O5的Ag-NiFe2O4/NiO样品在Na3AlF6-5?F2-5%Al2O3熔体中的腐蚀行为.研究表明:无添加剂的样品有较明显的腐蚀迹象,而添加2.0%V2O5的样品腐蚀后尺寸略有变化,表现出很好的耐腐蚀性.对腐蚀后样品的表面进行扫描电镜/能量色散X射线分析发现:在添加剂V2O5的作用下,Fe2O3在冰晶石中的溶解速率减小,从而抑制了陶瓷基体的溶解.另外,无添加剂样品表面各元素分布不均匀,说明无添加剂的样品在电解过程中发生选择性腐蚀,晶界等薄弱部位先被腐蚀.而添加了2.0%V2O5的样品中各元素分布均匀,说明V2O5增强了晶界的稳定性,提高了材料抗电解质的腐蚀能力.     

NiFe2O4惰性阳极的制备及其电解腐蚀机理

以Fe2O3和NiO为主要原料,添加2%(按质量计)MnO2,采用固相烧结工艺制备了NiFe2O4惰性阳极.用X射线衍射和扫描电子显微镜对材料的组成和微观结构进行了研究,测量了样品在冰晶石熔盐中不同电流密度下的电解腐蚀速率,并对其腐蚀机理作了初步探讨.结果表明:惰性阳极由NiO和NiFe2O4尖晶石两相组成,MnO2作为固溶体在尖晶石晶界处富集.电解腐蚀呈现出物理化学溶解过程,熔盐对试样的电解腐蚀首先要在晶界处发生反应生成更稳定的FeAl2O4相,而FeAl2O4相结构致密,冰晶石熔盐通过该相向NiFe2O4尖晶石晶粒内扩散速度减慢,从而降低了腐蚀速率.     

NiFe2O4隋性阳极的制备及其电解腐蚀机理

以Fe2O3和NiO为主要原料，添加2％（按质量计）MnO2，采用固相烧结工艺制备了NiFe2O4惰性阳极。用X射线衍射和扫描电子显微镜对材料的组成和微观结构进行了研究，测量了样品在冰晶石熔盐中不同电流密度下的电解腐蚀速率，并对其腐蚀机理作了初步探讨。结果表明：惰性阳极由NiO和NiFe2O4尖晶石两相组成，MnO2作为固溶体在尖晶石晶界处富集。电解腐蚀呈现出物理化学溶解过程，熔盐对试样的电解腐蚀首先要在晶界处发生反应生成更稳定的FeAl2O4相，而FeAl2O4相结构致密，冰晶石熔盐通过该相向NiFe2O4尖晶石晶粒内扩散速度减慢，从而降低了腐蚀速率。     

ZrO2(f)-NiFe2O4惰性阳极在冰晶石熔盐中的腐蚀行为

以NiO和Fe2O3为原料,采用固相烧结法合成了NiFe2O4尖晶石,通过添加ZrO2纤维[ZrO2(f)]制备了ZrO2(f)-NiFe2O4惰性阳极材料. 采用失重法测量了阳极试样在冰晶石熔盐中的静态热腐蚀率和电解腐蚀率,并对腐蚀机理进行了探讨. 结果表明,ZrO2(f)添加量由0增加至4%(w)时,阳极试样的气孔率从4.9%上升到5.8%,导致其静态热腐蚀率由3.8 mg/(cm2×h)增大到4.3 mg/(cm2×h);在电场作用下,氧化物在冰晶石熔盐中的溶解反应受到抑制,含3%(w) ZrO2(f)阳极试样的电解腐蚀率为2.2 mg/(cm2×h),远小于其静态腐蚀率,腐蚀均为物理化学溶解过程;高温下ZrO2(f)在冰晶石熔盐中稳定性良好,可作为铝电解NiFe2O4基惰性阳极的强韧化材料.     

NiFe2O4/Ag惰性阳极的熔盐腐蚀性能

以Fe2O3,NiO和Ag粉为主要原料,采用固相烧结工艺制备了NiFe2O4/Ag惰性阳极.采用X射线衍射和扫描电子显微镜对材料的组成和微观结构进行了研究,并测量了样品抗热震性、抗折强度、在冰晶石熔盐中的静态热腐蚀以及电解腐蚀速率,对其腐蚀过程作了初步探讨.结果表明:惰性阳极由NiO,NiFe2O4尖晶石和Ag三相组成.随着金属Ag含量的增多,惰性阳极样品在冰晶石熔盐中的静态热腐蚀速率增加,由于抗热震性和抗折强度有了大幅提高,电解腐蚀速率降低.静态热腐蚀和电解腐蚀呈现出物理化学溶解过程,而且由于金属银对晶界的强化作用,电解腐蚀由晶粒开始.     

纯Fe在酸性AlCl_3-EMIC离子液体中的阳极行为

重点研究了纯铁(Fe)在2∶1酸性AlCl_3-氯化1-甲基-3-乙基咪唑(AlCl_3-EMIC)中的阳极行为。通过三电极体系测定了Fe在AlCl_3-EMIC中的阳极极化和不同电位下的电流-时间曲线,利用恒电位溶解计算了Fe溶解的价态,最后通过扫描电子显微镜(SEM)观察了不同电流密度下Fe的溶解形貌。结果表明:Fe表面的氧化膜会阻碍Fe的溶解,在去除氧化膜后,当电位达到-0.35V时,Fe开始发生活性溶解,产物为Fe(Ⅱ)。Fe的阳极电流密度随电位的增加而增加,达到峰值后显著下降。小电流密度下(如2mA·cm~(-2)),Fe的溶解形貌随时间的延长,呈现先点状腐蚀再均匀腐蚀的特点;而大电流密度下(如15mA·cm~(-2)),Fe电极表面会生成一层固态物质,同时可见清晰的划痕,即不发生明显的腐蚀。     

MnO2添加剂对镍铁尖晶石基惰性阳极耐腐蚀性的影响

以氧化物NiO和Fe2O3为原料,添加氧化物MnO2,采用高温固相烧结法制备了NiFe2O4基惰性阳极材料,采用失重法测量了阳极试样的静态热腐蚀速率,并对其腐蚀机理进行了初步探讨. 实验结果表明,添加2%(ω) MnO2粉末的惰性阳极试样的静态热腐蚀速率最低. 由于掺杂的MnO2在晶界处富集,熔盐对晶粒的腐蚀首先在晶界处发生反应生成Mn2AlO4相,而Mn2AlO4相结构致密,冰晶石熔盐通过该相向NiFe2O4尖晶石晶粒内扩散速度减慢,从而降低了腐蚀速率.     

La_2O_3掺杂对金属陶瓷显微结构与性能的影响

采用冷压烧结技术制备La2O3掺杂17Ni/(NiFe2O4-10NiO)金属陶瓷惰性阳极材料,研究了La2O3掺杂对材料显微结构、烧结致密化、抗高温氧化性能及耐熔盐腐蚀性能的影响。结果表明:La2O3与陶瓷相反应生成FeLaO3相,活化了NiFe2O4晶格,促进材料的烧结致密化。适量掺杂La2O3可减少氧化膜及氧化层孔洞产生,防止出现氧化膜裂纹,提高抗高温氧化性能。La2O3掺杂的金属陶瓷通过与外界熔盐生成稳定、致密的腐蚀反应层,使基体材料得到保护,减缓腐蚀速率。La2O3掺杂量为1.0%时,腐蚀速率仅为1.336 7×10--3 g/(cm2·h)。     

纯Fe在酸性AlCl3-EMIC离子液体中的阳极行为

重点研究了纯铁（Fe）在2∶1酸性AlCl₃-氯化1-甲基-3-乙基咪唑（AlCl₃-EMIC）中的阳极行为。通过三电极体系测定了Fe在AlCl₃-EMIC中的阳极极化和不同电位下的电流-时间曲线,利用恒电位溶解计算了Fe溶解的价态,最后通过扫描电子显微镜（SEM）观察了不同电流密度下Fe的溶解形貌。结果表明：Fe表面的氧化膜会阻碍Fe的溶解,在去除氧化膜后,当电位达到-0.35 V时,Fe开始发生活性溶解,产物为Fe（Ⅱ）。Fe的阳极电流密度随电位的增加而增加,达到峰值后显著下降。小电流密度下（如2 mA·cm^-2）,Fe的溶解形貌随时间的延长,呈现先点状腐蚀再均匀腐蚀的特点;而大电流密度下（如15 mA·cm^-2）,Fe电极表面会生成一层固态物质,同时可见清晰的划痕,即不发生明显的腐蚀。     

酚类电氧化聚合法合成聚苯醚

<正> 2,6-二甲酚可以铜胺络合物为催化剂,在室温下与氧反应,生成聚2,6-二甲基1,4-苯撑氧(聚苯醚)。此聚合反应电可在阳极氧化下进行。同时放出等当量的氢。作者最近发现,酚类在适当电解条件下可以电氧化生成聚2,6-二取代基苯撑氧。聚合用电解装置的特点是:单室电解槽,电极间无隔膜,溶剂选用聚合物和支持电解质均可溶解,且在电解条件下也比较稳定的二氯甲烷、硝基苯和氢醌二甲醚等。本实验是用三对铂电极(2×5cm)作为电解的工作电极和副电极串联,电极间距离为1mm。参比电极为Ag—AgCl。槽中加入50ml溶液,含0.005摩尔的玢和0.01摩尔的支持电解质(如四乙基溴     

NiFe2O4-M金属陶瓷惰性阳极成分设计的热力学分析

NiFe2O4-M金属陶瓷惰性阳极由氧化物陶瓷相和金属相组成.多数美国专利认为Fe,Ni,Cu,Co,Ti,Cr,Mn,Al,Pd,Ag,V,Zr,Y,La,Ta,Nb,Sc,Hf,Ca,Sn,Zn等21种金属均适合作为上述阳极的金属相成分.但文中的热力学详细分析计算结果表明:在上述前8种金属中,仅有Cu,Ni 2种适...     

Al2O3-M金属陶瓷惰性阳极及铝电解实验

所研制的惰性阳极成分为Al2O3+Y2O3+CeO2+(Fe-Ni+Y)。其中Al2O3和稀土氧化物微米粉经高能球磨细化到50~300 nm的纳米/准纳米级,再与-125μm的Fe-Ni-Y金属粉末混合,进行普通球磨,产出的混合粉经机械压制或冷等静压成型,烧结成为惰性阳极。该惰性阳极在常规冰晶石-氧化铝电解质中接受30h的铝电解实验考察,用电子探针和X射线衍射仪(XRD)对阳极横断面进行结构分析和元素微区分布分析,结果表明:阳极的电阻小于0.5Ω,推算所得的阳极腐蚀速率为14mm/a,电解出的原铝达到Al 99.00标准(GB/T1196—2002)。实验还发现,与微米氧化物金属陶瓷阳极相比,这类纳米/准纳米氧化物金属陶瓷惰性阳极有更佳的可成型性、烧结性、导电性和抗腐蚀性能,压制的成功率在95%以上(而微米氧化物阳极仅在65%左右),且不易产生烧结裂纹等。     

An experimental study of aluminium electrowinning using a nickel-based hydrogen diffusion anode

Laboratory scale electrolysis experiments were conducted to investigate the electrowinning of aluminium using hydrogen diffusion anodes. A potassium-based electrolyte (KF–AlF₃–Al₂O₃), porous nickel alloy anode and molybdenum disk cathode were used in experiments at 750 °C. Hydrogen gas was supplied to the anode/electrolyte interface through the porous anode. Experiments were conducted in potentiostatic, galvanostatic and galvanodynamic modes. There was a measurable depolarisation of the anode potential and also anode reaction of hydrogen and oxygen ions in the bath to form water vapour was confirmed by the water vapour condensate found at the electrolysis exit gas pipe. Metallic aluminium was found on the spent cathode. The experiments conducted in the galvanodynamic mode suggested that the rate limiter for hydrogen oxidation was the availability of surface hydrogen at the anode/electrolyte interface. The anode surface corroded during electrolysis and impurities were found both in the molten bath and on the cathode.     

掺杂MnO2对铁酸镍陶瓷惰性阳极性能的影响

为了提高铝电解惰性阳极材料的性能,尝试在合成铁酸镍陶瓷阳极的过程中掺杂一定量MnO2. 采用高温固相反应法在1200℃下烧结6 h,制备了掺杂MnO2的铁酸镍阳极材料. 对掺杂试样进行X射线衍射分析,并且研究了掺杂MnO2对材料密度、导电性及抗弯强度和抗热震性的影响. 研究结果表明,掺杂MnO2后未形成新相,MnO2与NiFe2O4形成固溶体,Mn4+离子取代了部分Fe3+离子,材料仍是镍铁尖晶石结构;掺杂MnO2后,NiFe2O4的晶格产生畸变,说明MnO2促进了烧结,提高了材料的密度;并且由于Mn4+离子取代Fe3+离子,产生阳离子空位,改善了铁酸镍阳极的导电性. 同时MnO2对改善试样的抗弯强度及抗热震性也有明显作用.     

On the development of metallic inert anode for molten CaCl2–CaO System

Some fundamental aspects related to inert anode development in molten CaCl₂–CaO were investigated based on thermodynamic analysis, electrochemistry of metals and solubility of oxide measurements. The Gibbs free energy change of several key anodic reactions including electro-stripping of metals, electro-formation of metallic oxides, electro-dissolution of metallic oxides as well as oxygen and chlorine evolution was calculated and documented, for the first time, as a reference to develop metallic inert anode in chloride based melts. The anodic behaviors of typical metals (Ni, Fe, Co, Mo, Cu, Ag, and Pt) in the melt were investigated. The results confirmed the thermodynamic stability order of metals in the melts and revealed that surface oxide formation can increase the stability of the electrodes in CaO containing melt. Furthermore, solubility of several oxides (NiO, Fe₂O₃, Cr₂O₃, Co₃O₄, NiFe₂O₄) in pure CaCl₂ or CaCl₂–CaO melts was measured to evaluate the stability of oxide coating or a cermet inert anode in the melt. It was found that the solubility of NiO decreased with increasing CaO concentration, while that of Fe₂O₃ increased. Ni coated with NiO film had much higher stability during anodic polarization.     

中温H2S-空气燃料电池阴极催化剂的研究

Abstract Cathode catalysts comprising composite NiO, NiO-Pt, or LiNiO2 have been developed for electro- chemical oxidation of hydrogen sulfide in intermediate-temperature solid oxide fuel cells （ITSOFCs）. All catalysts exhibited good electrical conductivity and catalytic activity at operating temperature. Composite NiO catalysts were found to be more active and have lower over potential and higller current density than pure Pt although the electrical conductivity of NiO itself is lower than that of Pt. This problem has been overcome by either admixing as high as 10% （by mass）Ag powder into NiO_ cathode layer or using composite NiO c atalysts such as NiO-Pt and LiNiO2 catalysts. Composite catalysts like NiO with Ag, electrolyte and starch admixed, NiO-Pt, which was prepared from a mixture of NiO and Pt powders, by admixing electrolyte and starch, and LiNiO2, which is derived from the reaction of LiOH-H2O and NiO with electrolyte and starch admix_ed have been shown to be feasible and effective in an intermediate-temperature H2S-air fuel cell. A fuel cell using Li2SO4-based proton-conducting membrane as electrolyte, metal sulfides as anode catalysts, and composite NiO as cathode catalysts produced a maximum current density about 300mA·cm^-2 and maximum power density over 80 mW-cm-2 at 680℃.