100 W-class green hydrogen production from ammonia at a dual-layer electrode containing a Pt-Ir catalyst for an alkaline electrolytic process

Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).

Development of a novel electrolytic process for producing high-purity magnesium metal from magnesium oxide using a liquid tin cathode

The current electrolytic processes for magnesium(Mg)metal have several disadvantages,such as anhydrous magnesium chloride(MgCl_(2))preparation and generation of harmful chlorine(Cl_(2))gas.To overcome these drawbacks,a novel Mg production process to produce high-purity Mg metal directly from magnesium oxide(MgO)was investigated in this study.The electrolysis of MgO was conducted using a liquid tin(Sn)cathode and a carbon(C)anode in the eutectic composition of a magnesium fluoride(MgF_(2))-lithium fluoride(LiF)molten salt under an applied voltage of 2.5 V at 1053-1113 K.Under certain conditions,the Mg-Sn alloys with Mg_(2)Sn and Mg(Sn)phases were obtained with a current efficiency of 86.6%at 1053 K.To produce high-purity Mg metal from the Mg-Sn alloy,vacuum distillation was conducted at 1200-1300 K for a duration of 5-10 h.Following the vacuum distillation,the concentration of Mg in the Mg-Sn alloy feed decreased from 34.1 to 0.17 mass%,and Mg metal with a purity of 99.999%was obtained at 1200 K.Therefore,the electrolytic process developed here is feasible for the production of high-purity Mg metal from MgO using an efficient method.

Processing-Microstructure Relationships in the Plasma Electrolytic Oxidation (PEO) Coating of a Magnesium Alloy

In the plasma electrolytic oxidation (PEO) coating of light metal alloys, changing the electrical parameters and electrolytic composition can change the discharge behaviour and, ultimately, the thickness, surface morphology and porosity of the coating. In the present study a combination of cathodic and anodic current pulses with suitable Ton and Toff periods were used to control the porosity and other structural defects of PEO coatings of an AM60B magnesium alloy. In order to investigate the effect of a current mode on the plasma discharge behaviour and coating microstructure during the PEO treatment of magnesium alloy, the emission intensities of six different spectral lines from the plasma species were recorded simultaneously as a function of both time and current mode using optical emission spectroscopy (OES) system. The fluctuations in signal intensities and temperature during the coating process reflect differences in location of both the discharge initiation, and discharge type. The coating surface morphology and microstructure that are obtained can be linked to the plasma discharge behavior. These results are discussed in relation to the discharge behaviour, and how such changes in discharge behaviour relate to the coating mechanisms.

Methanol oxidation in acidic and alkaline electrolytes using PtRuIn/C electrocatalysts prepared by borohydride reduction process

PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.

Growth and Corrosion Characteristics of Plasma Electrolytic Oxidation Ceramic Films Formed on AZ31 Magnesium Alloy

The growth characteristics of oxide ceramic films formed on AZ31 magnesium alloy with plasma electrolytic oxidation (PEO) technique in alkaline silicate solution were investigated. The composition, structure and morphology of the coatings were detected by energy dispersive X-ray spectroscope and scanning electron microscope. The amount of dissolved magnesium in the electrolytes during PEO process was measured by atomic absorption spectrometry. The results indicated that the growth process of PEO films had three stages when applied with constant voltage mode. In the first stage, the growth rate of PEO films was low, and concentrations of elements O, Mg and Si varied slightly. After sparking occurred (the second stage), the PEO films showed higher growth rate due to the high transfer rate of ions and electrons, and the existence of plasma reactions. When the growth rate tended to maintain stable with time, the third stage happened. PEO films exhibited different uniform and pitting-corrosion characteristics in different reaction stages. The films formed at 300 V for 30 min performed best corrosion resistance and the phase of ceramic films was mainly composed of MgSiO3 and forsterite Mg2SiO4.

Direct oxidation of methane at low temperature using Pt/C,Pd/C,Pt/C-ATO and Pd/C-ATO electrocatalysts prepared by sodium borohydride reduction process

The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25 ℃ and in a direct methane proton exchange membrane fuel cell at 80 ℃. The electrocatalysts prepared also were characterized by X-ray diffraction( XRD) and transmission electron microscopy( TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic( fcc) structure,and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic( fcc) structure. For Pt/C-ATO and Pd/C-ATO,characteristic peaks of cassiterite( SnO_2) phase are observed,which are associated with Sb-doped SnO_2( ATO) used as supports for electrocatalysts. Cyclic voltammograms( CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However,this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism,where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR( Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed,which indicates the production of carbon dioxide. Polarization curves at 80 ℃in a direct methane fuel cell( DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.

电力储能用钠离子电池失效机理及性能提升分析

钠离子电池是未来锂离子电池的有效替代品,其能否实现快速产业化,不仅需要大的容量,还需要高安全性。本研究从失效模式、失效机理和高安全型钠离子电池开发三者的关系入手,将电池整体的失效简化为不同组成部分的失效,对钠离子电池的正极、负极、电解质、隔膜等部件进行了失效分析和总结,然后提出了一些避免失效和性能提升的方法,最后对钠离子电池失效分析的检测方法进行了介绍,并给出了简单的可供参考的流程设计。

The Properties of YSZ Electrolyte Sintering at 1300 ℃

The properties of yttria stabilized zirconia（YSZ） related to the sintering process were discussed.YSZ nano-powders about 40-100 nm as raw material,the sub-micrometer grain sizes such as 0.4-3 μm in YSZ were gotten by sintering process at 1300 ℃,which was performed at 1000 ℃ for 2 h,then raised the temperature at the rate of 50 ℃ / h to 1400 ℃,then decreased directly to 1300 ℃ in 30 minutes,finally at 1300 ℃ for 5-20 hours.The ratio of bigger grain size becomes larger as the holding time increasing at 1300 ℃.The grains less than 1 μm are about 50%,eg,43.2%,52.2% and 51.1% related to 1300 ℃ holding 5 hours,8 hours and 10 hours,respectively.As YSZ grain size became small,the electrical conductivities did not decrease,even increased,about 0.20 s/cm at 1000 ℃.The reduced sintering temperature and time were benefited to co-fire with the electrodes in electrode-supported SOFCs.

Effect of Initial Oxide Film on the Formation and Performance of Plasma Electrolytic Oxidation Coating on 7075 Aluminum Alloy

In the early stage of plasma electrolytic oxidation(PEO),the quick formation of the initial oxide film on the surface of the aluminum substrate is necessary for the subsequent discharge spark process.Furthermore,the compactness of the initial oxide film greatly affects the quality of the PEO coating,but the related mechanisms are not investigated in detail.In this paper,the status of the initial oxide film was adjusted by adding the(NaPO)into the based electrolyte,and then the effect of initial oxide film on the formation of the PEO coating was compared.Microstructure and chemical composition were analyzed by scanning electron microscope,transmission electron microscopy and X-ray photoelectron spectrometer.The compactness of the initial oxide film was characterized by Mott-Schottky plots.The corrosion resistance was measured by electrochemical impedance spectroscopy.The results show that the addition of(NaPO)can promote the co-deposition of phosphide compound into the initial oxide film and improve the film compactness,which is beneficial for the more uniform spark discharge in the later stage.As a result,the addition of(NaPO)is helpful to obtain PEO coating with better performance.

Pressureless reactive sintering mechanism of nanocrystalline Bi_2O_3-Y_2O_3 solid electrolyte

The nanocrystalline Bi2O3-Y2O3 solid electrolyte material was synthesized by pressureless reactive sintering process with Bi2O3 and Y2O3 nano mixed powder as raw materials, which was prepared by a chemical coprecipitation process. The study on the behavior of nano δ-Bi2O3 formation and its grain growth showed that the solid solution reaction of Y2O3 and δ-Bi2O3 to form δ-Bi2O3 occurs mainly in the initial stage of sintering process, and nano δ-Bi2O3 crystal grains grow approximately following the rule of paracurve （（D-D0）^2=K.t） during sintering process. After sintered at 600℃ for 2 h, the samples could reach above 96% in relative density and have dense microstructure with few remaining pores, the δ-Bi2O3 grains are less than 100 nm in size.

在线电解修锐砂轮氧化膜界面反应及复合磨粒形成机理

Electrolytic In-process Dressing(ELID)砂轮氧化膜具有辅助抛光性能,对改善磨削表面质量具有极其重要意义。分析了ELID砂轮表面氧化膜界面反应及复合磨粒的形成机理,利用X-射线衍射(μ-XRD)微区分析及电子能谱仪(XPS)对复合磨粒的组成成分、复合区域进行了测试,用扫描电镜(SEM)和透射电镜(TEM)对其形状、粒度、微观结构进行了研究。研究表明,氧化膜中复合磨粒是以磨粒为中心,从中心到边缘的成分依次为α-Fe_(2)O_(3),γ-Fe_(2)O_(3),FeO(OH),Fe(OH)3等氧化物的复合结构。复合磨粒表面形成的氧化膜,呈层层堆积的圆葱状结构,磨削脱水后呈龟背状裂纹。复合磨粒形状为近似长圆形,粒度可达11.5μm到50μm。若干个复合磨粒在氧化膜内连续成网状结构,该网状结构对氧化膜辅助抛光有利,复合磨粒有效去除宽度为磨粒粒度及α-Fe_(2)O_(3)层宽度。

Use of various MgO resources for high-purity Mg metal production through molten salt electrolysis and vacuum distillation

A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.

Production of high-purity Mg metal from dolomite through novel molten salt electrolysis and vacuum distillation

In this study,a novel Mg production process for producing high-purity Mg metal from dolomite was developed.When the electrolysis of calcined dolomite was conducted using Cu cathode and C anode in MgF_(2)–LiF molten salt at 1083–1173 K by applying an average current of 1.42–1.46 A for 9.50–21.0 h,the current efficiency of 66.4–88.6%was obtained.The produced Mg alloys consisted of MgCu_(2)and Cu(Mg)or MgCu_(2)and CuMg_(2)phases,depending on the Mg concentration in the Mg alloy.When the electrolysis of calcined dolomite was conducted in MgF_(2)–LiF–CaF_(2)molten salt at 1083 K,the current efficiency was 40.9–71.4%,owing to undesired reactions such as electroreduction of Ca^(2+)or/and CO_(3)^(2−)ions.Meanwhile,the current efficiency increased from 40.9%to 63.2%by utilizing a Pt anode,because the occurrence of CO_(3)^(2−)ions in the molten salt was prevented.After vacuum distillation of the obtained Mg alloys at 1300 K for 10 h,Mg metal with a purity of 99.9996–99.9998%was produced.Therefore,the feasibility of this novel process for the production of high-purity Mg metal from dolomite was demonstrated.

新型电解精炼高纯金试验研究

针对王水提金法生产技术瓶颈,采用隔膜电解工艺作为高纯金的生产工艺,利用电解金泥、湿法金泥、合质金作为原料进行了试验研究。结果表明:采用电解金泥时,生产的产品Au<99.999%;采用湿法金泥时,可产出合格的高纯金;合质金Au品位90%左右时,生产的产品Au>99.999%,但Ag、Cu元素超过了高纯金标准;综合试验控制Au在95%时,可产出合格的高纯金,且23项杂质元素全部达到高纯金标准。隔膜电解工艺整个过程由PLC自动控制相较传统电解工艺电解周期由40 h减少到24 h,自动化程度高,无氮氧化物产生,可实现金阳极板溶解与金电积同时进行,金残余小于10 mg/L。

中温固体氧化物燃料电池制备进展

介绍了制备中温固体氧化物燃料电池(SOFC)薄膜的各种工艺方法及制备中温单电池(PEN)的复合工艺。

支持电解质对酸性大红染料废水电解的影响

通过静态试验对比研究了模拟酸性大红3R染料废水在NaCl和Na2SO4体系中的电化学氧化过程,考察了电流密度、电解质浓度和初始pH对色度去除效果的影响,比较了两种电解质对染料废水的处理效果。结果表明,在不同支持电解质体系中,电流密度、电解质浓度和初始pH对染料废水脱色作用的影响具有基本相同的规律;在不同支持电解质体系中,染料废水降解效果差别很大,以NaCl为支持电解质时的脱色率明显高于以Na2SO4作为支持电解质。

铝电解电容器阳极氧化铝膜的耐水合处理

分析了氧化铝的水合作用机理、不同pH介质溶液中氧化铝的表面性能以及阳极氧化形成过程中水合氧化物的生成。结果表明:耐水合剂与氧化铝表面作用应形成一定的特征,才能起到很好的耐水合作用,不同类型的耐水合剂,其耐水合机理也不同。介绍了国内外有关氧化铝耐水合处理的研究现状和发展趋势,并提出了有待改善现行耐水合处理试剂、工艺和测试方法的问题。

新型全固态复合聚合物电解质的制备与应用

高分子聚合物与碱金属盐的络合物具有离子导电性,是电化学材料领域在过去25年里的重要发现之一,它的发现揭开了人们研究固体电解质的序幕。高分子全固态复合电解质由于具有良好的离子传输能力、成膜性能和力学性能,已成为电致变色器件等电化学装置中的重要组成部分。总结了聚合物电解质的种类,电导率的影响因素与表征方法,分析了全固态聚合物电解质材料的制备工艺与应用。新型复合聚合物电解质材料具有很好的市场前景和十分明显的社会经济效益,对此课题的进一步深入研究和技术上的突破有可能导致新能源材料领域,尤其是电池材料领域的一场新的技术革命。

准毛细间隙反应器中直接电氧化合成茴香醛二甲基缩醛

以准毛细间隙反应器为电化学合成装置，采用恒电流电解技术考察了阳极材料、支持电解质、电流密度等工艺参数对茴香醚直接电氧化合成茴香醛二甲基缩醛的影响。结果表明，收率从高到低采用的阳极材料依次为：石墨＞钛基铱钽＞钛基钌铱＞钛基铂；支持电解质依次为：对甲基苯磺酸钠＞苯磺酸钠＞氟化钾＞甲醇钠＞高氯酸钠＞间硝基苯磺酸钠；在电流密度1～9 A·dm-2范围内，反应选择性随着电流密度的增大而减小；添加适量的2,6-二甲基吡啶能抑制茴香醛二甲基缩醛的氧化从而提高反应选择性。在优化条件下，茴香醛二甲基缩醛的收率和电流效率分别达到75%和47%。

在线电解修整磨削液研究现状及其展望

在线电解修整(electrolytic in-process dressing,ELID)镜面磨削过程中,磨削液的成份及配比对砂轮表面氧化膜的生成速度、致密性、黏附性以及绝缘性等都有着很大的影响,磨削液的配比及优化成为ELID磨削过程中的关键技术之一。主要介绍了ELID磨削液的成分配比、磨削液对氧化膜的影响以及ELID磨削液改进这几个方面的研究进展,并对ELID磨削液下一步的研究重点进行了展望。