DH-101型微量氧分析仪的研制

介绍了一种新的用于工业流程微量氧分析的仪器。最小县程为0～2×10－6。说明了仪器的结构、工作原理和设计特点。传感器采用对氧敏感的三电极结构原电池，性能稳定，响应速度快，工作寿命长，校准方便。经性能测试和现场实际应用，证明仪器性能稳定可靠，灵敏度高，能满足现场分析的需要。

血气分析技术(系列讲座之五)

血气分析技术（系列讲座之五）北京医疗器械研究所余拔章（二）电流法在前述的电位法中，电动势测量是在电池没有电流通过或电流极小的情况下进行的，电极基本上处于一种平衡状态。而电流法则要求给电解池施加外加电压，并同时测量由此引起的电化学反应过程所产生的电流。...

Composite Cathode based on Mn-doped Perovskite Niobate-Titanate for Efficient Steam Electrolysis

Redox-active Mn is introduced into the B site of redox-stable perovskite niobate-titanate to improve the electrocatalytic activity of composite cathode in an oxide-ion-conducting solid oxide electrolyzer. The XRD and XPS results reveal the successful partial replacement of Ti/Nb by Mn in the B site of niobate-titanate. The ionic conductivities of the Mndoped niobate-titanate are significantly improved by approximately 1 order of magnitude in reducing atmosphere and 0.5 order of magnitude in oxidizing atmosphere compared with bare niobate-titanate at 800 ℃. The current efficiency for Mn-doped niobate-titanate cathode is accordingly enhanced by ,-25% and 30% in contrast to the bare cathode with and without reducing gas flowing over the cathode under the applied voltage of 2.0 V at 800 ℃ in an oxide-ion-conducting solid oxide electrolyzer, respectively.

Effect of Gd_(0.2)Ce_(0.8)O_(1.9) nanoparticles on the oxygen evolution reaction of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ) anode in solid oxide electrolysis cell

La（0.6）Sr（0.4）Co（0.2）Fe（0.8）O（3-δ）（LSCF） anodes were infiltrated by Gd（0.2）Ce（0.8）O（1.9）GDC） nanoparticles to improve the oxygen evolution reaction（OER） performance of solid oxide electrolysis cells（SOECs） in CO2 electroreduction. The effect of GDC loading was investigated, and 10 wt% GDC nanoparticle infiltration of the LSCF（10 GDC/LSCF） anode results in the highest OER performance. Electrochemical impedance spectra measurements indicate that the infiltration by GDC nanoparticles greatly decreases the polarization resistance of the SOECs with the 10 GDC/LSCF anodes. The following distribution of relaxation time analysis suggests that four individual electrode processes are involved in the OER and that all of them are accelerated on the 10 GDC/LSCF anode. Three phase boundaries, surface oxygen vacancies, and bulk oxygen mobility increased, based on scanning electron microscopy and temperature-programmed desorption of O2 characterizations, and contributed to the enhancement of the four electrode processes of the OER and electrochemical performance of SOECs.

Highly dispersed nickel species on iron‐based perovskite for CO_(2) electrolysis in solid oxide electrolysis cell

Feasible construction of cathode materials with highly dispersed active sites can extend the tri‐ple‐phase boundaries,and therefore leading to enhanced electrode kinetics for CO_(2) electrolysis in solid oxide electrolysis cell(SOEC).Herein,highly dispersed nickel species with low loading(1.0 wt%)were trapped within the La_(0.8)Sr_(0.2)FeO_(3)–δ‐Ce_(0.8)Sm_(0.2)O_(2)–δvia a facial mechanical milling ap‐proach,which demonstrated excellent CO_(2) electrolysis performance.The highly dispersed nickel species can significantly alter the electronic structures of the LSF‐SDC without affecting its porous network and facilitate oxygen vacancy formation,thus greatly promote the CO_(2) electrolysis perfor‐mance.The highest current density of 1.53 A·cm^(-2) could be achieved when operated under 800℃ at 1.6 V,which is about 91%higher than the LSF‐SDC counterpart.

Effects of current density on preparation of grainy electrolytic manganese dioxide

Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrographs measurements. Current density has important effects on cell voltage, anodic current efficiency and particle size of the grainy electrolytic manganese dioxide, and the optimum current density is 30 A/dm2. The grainy electrolytic manganese dioxide electrodeposited under the optimum conditions consists of γ-MnO2 with an orthorhombic lattice structure; the grainy electrolytic manganese dioxide has a spherical or sphere-like appearance and a narrow particle size distribution with an average particle diameter of 7.237 μm.

Electrochemical conversion of C1 molecules to sustainable fuels in solid oxide electrolysis cells

Stimulated by increasing environmental awareness and renewable-energy utilization capabilities,fuel cell and electrolyzer technologies have emerged to play a unique role in energy storage,conversion,and utilization.In particular,solid oxide electrolysis cells(SOECs)are increasingly attracting the interest of researchers as a platform for the electrolysis and conversion of C1 molecules,such as carbon dioxide and methane.Compared to traditional catalysis methods,SOEC technology offers two major advantages:high energy efficiency and poisoning resistance,ensuring the long-term robustness of C1-to-fuels conversion.In this review,we focus on state-of-the-art technologies and introduce representative works on SOEC-based techniques for C1 molecule electrochemical conversion developed over the past several years,which can serve as a timely reference for designing suitable catalysts and cell processes for efficient and practical conversion of C1 molecules.The challenges and prospects are also discussed to suggest possible research directions for sustainable fuel production from C1 molecules by SOECs in the near future.

Enhancing storage performance of P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)cathode materials by Al_(2)O_(3)coating

The P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)materials were synthesized by an ultrasonic spray pyrolysis followed by solid-state sintering method.The structures,morphologies and electrochemical performances of Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)materials were characterized thoroughly by means of X-ray diffractometer,scanning electron microscope and electrochemical charge/discharge instruments.Moreover,a thin layer of Al_(2)O_(3),which was formed on the surface of Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2),can enhance the storage performance by preventing the formation of Na_(2)CO_(3)·H_(2)O,which is believed to enhance the electrochemical performances of Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)materials.This facile surface modification method may pave a way to synthesize advanced cathode materials for sodium-ion batteries.

Electrocatalysts development for hydrogen oxidation reaction in alkaline media:From mechanism understanding to materials design

Anion exchange membrane(AEM)fuel cells have gained great attention partially due to the advantage of using non-precious metal as catalysts.However,the reaction kinetics of hydrogen oxidation reaction(HOR)is two orders of magnitude slower in alkaline systems than in acid.To understand the slower kinetics of HOR in base,two major theories have been proposed,such as(1)pH dependent hydrogen binding energy as a major descriptor for HOR;and(2)bifunctional theory based on the contributions of both hydrogen and hydroxide adsorption for HOR in alkaline electrolyte.Here,we discuss the possible HOR mechanisms in alkaline electrolytes with the corresponding change in their Tafel behavior.Apart from the traditional Tafel-Volmer and Heyrovsky-Volmer HOR mechanisms,the recently proposed hydroxide adsorption step is also discussed to illustrate the difference in HOR mechanisms in acid and base.We further summarize the representative works of alkaline HOR catalyst design(e.g.,precious metals,alloy,intermetallic materials,Ni-based alloys,carbides,nitrides,etc.),and briefly describe their fundamental HOR reaction mechanism to emphasize the difference in elementary reaction steps in alkaline medium.The strategy of strengthening local interaction that facilitates both H2 desorption and Hads+OHads recombination is finally proposed for future HOR catalyst design in alkaline environment.

Coupling Heat and Electricity Sources to Intermediate Temperature Steam Electrolysis

The use of CO2-free energy sources for running SOEC （solid-oxide electrolysis cell） technologies has a great potential to reduce the carbon dioxide emissions compared to fossil fuel based technologies for hydrogen production. The operation of the electrolysis cell at higher temperature offers the benefit of increasing the efficiency of the process. The range of the operating temperature of the SOEC is typically between 800 ~C and 1,000 ~C. Main sources of degradation that affect the SOEC stack lifetime is related to the high operating temperature. To increase the electrolyser durability, one possible solution is to decrease the operating temperature down to 650 ~C, which represents the typical operating range of the ITSE （intermediate temperature steam electrolysis）. This paper is related to the work of the JU-FCH project ADEL, which investigates different carbon-free energy sources with respect to potential coupling schemes to ITSE. A predominant focus of the analysis is put on solar concentrating energy systems （solar tower） and nuclear energy as energy sources to provide the required electricity and heat for the ITSE. This study will present an overview of the main considerations, the boundary conditions and the results concerning the development of coupling schemes of the energy conversion technologies to the electrolyser.

Operational Robustness Studies of Solid Oxide Electrolysis Stacks

Stacks of solid oxide cells which can be run as both electrolysers and fuel cells have been tested for robustness towards simulations of stress conditions which are likely to occur during operation of solid oxide electrolysis systems, for which the energy supply comes from renewable sources, such as wind mills and solar cells. Such conditions are thermo mechanical stress conditions as well as loss of fuel and air supply. The cells have Ni/YSZ （yttria stabilized zirconia） fuel electrodes, YSZ electrolytes, and LSCF （lanthanum strontium cobalt ferrite） oxygen electrodes with a CGO （cerium gadolinium oxide） barrier layer. In the stacks, the cells are separated by chromium rich steel interconnects. The robustness tests of stacks are one step in the development of a SOEC （solid oxide electrolysis cell） core; the core component in a SOEC system, including one or more SOEC stacks, heaters, heat exchangers, insulation, and feed troughs.

1673K下SiO_2-CaO-MgO-Al_2O_3熔渣中Ni^(2+)的电化学行为

利用Mg O部分稳定的Zr O2固体电解质管集成构建Pt,O2(air)|Zr O2作参比电极的可控氧流电解池,采用循环伏安、方波伏安、计时电位、恒电位电解等电化学测试技术研究了1673 K高温下Si O2-Ca O-Mg O-Al2O3熔渣中Ni2+的电化学行为.结果表明,O2-在熔渣中的扩散和在Zr O2固体电解质内的电迁移不是熔渣中电活性物质还原的限制性环节,在本实验条件下利用构建的可控氧流电解池研究熔渣中Ni2+的电化学行为是可行的.熔渣中Ni2+在Ir电极上还原到Ni是受扩散控制的一步还原的可逆过程,利用循环伏安和计时电位测试技术所得数据计算得出了含有3%Ni O的熔渣中Ni2+的扩散系数分别为(3.50±0.18)×10-6和(2.80±0.22)×10-6cm2/s,与相关文献结果基本吻合.

1723K下熔渣中Ni^(2+)和Fe^(2+)离子共存时的电化学行为

利用MgO部分稳定的ZrO_2固体电解质管集成构建以Pt,O_2(空气)|ZrO_2作为参比电极的新型可控氧流电解池,采用循环伏安CV、方波伏安SWV、恒电位电解PE等方法,并结合热力学计算与显微观察、能谱分析,研究1 723K高温下SiO_2-CaO-MgO-Al_2O_3熔渣中共存的Ni^(2+)、Fe^(2+) 离子在Ir电极上的电化学行为。结果表明:熔渣系中FeO与NiO之间存在较弱的相互作用,但镍离子以Ni^(2+)存在,铁离子基本以Fe^(2+) 存在。进行方波伏安分析时,Ni^(2+)、Fe^(2+) 离子的还原峰电流对频率呈现不同的规律。Ni^(2+)在Ir电极上的电化学还原是扩散控制的一步两电子转移反应过程;Fe^(2+) 到Fe的电化学还原也是一步两电子转移反应过程,但Fe^(2+) 的还原明显受到Ni^(2+)还原的影响。基于循环伏安法,计算得到NiO、FeO的质量分数分别为3%、5%的熔渣中Ni^(2+)离子在1 723K下的扩散系数为(9.2±0.2)×10-6cm2/s。

Highly efficient overall urea electrolysis via single-atomically active centers on layered double hydroxide

Anodic urea oxidation reaction(UOR)is an intriguing half reaction that can replace oxygen evolution reaction(OER)and work together with hydrogen evolution reaction(HER)toward simultaneous hydrogen fuel generation and urea-rich wastewater purification;however,it remains a challenge to achieve overall urea electrolysis with high efficiency.Herein,we report a multifunctional electrocatalyst termed as Rh/Ni V-LDH,through integration of nickel-vanadium layered double hydroxide(LDH)with rhodium single-atom catalyst(SAC),to achieve this goal.The electrocatalyst delivers high HER mass activity of0.262 A mg^(-1) and exceptionally high turnover frequency(TOF)of 2.125 s^(-1) at an overpotential of100 m V.Moreover,exceptional activity toward urea oxidation is addressed,which requires a potential of 1.33 V to yield 10 mA cm^(-2),endorsing the potential to surmount the sluggish OER.The splendid catalytic activity is enabled by the synergy of the Ni V-LDH support and the atomically dispersed Rh sites(located on the Ni-V hollow sites)as evidenced both experimentally and theoretically.The selfsupported Rh/Ni V-LDH catalyst serving as the anode and cathode for overall urea electrolysis(1 mol L^(-1) KOH with 0.33 mol L^(-1) urea as electrolyte)only requires a small voltage of 1.47 V to deliver 100 mA cm^(-2) with excellent stability.This work provides important insights into multifunctional SAC design from the perspective of support sites toward overall electrolysis applications.

Tailored Sr-Co-free perovskite oxide as an air electrode for high-performance reversible solid oxide cells

Sr-Co containing perovskite oxides are prospective air electrode candidates for reversible solid oxide cells(RSOCs).However,their efficiencies are limited by Sr segregation and the high thermal expansion coefficient(TEC)of Cobased perovskites.Herein,La_(0.6)Ca_(0.4)Fe_(0.8)Ni_(0.2)O_(3-δ)(LCa FN)is tailored as an Sr-Co-free perovskite air electrode for highperformance RSOCs.Compared with La_(0.6)Sr_(0.4)Fe_(0.8)Ni_(0.2)O_(3-δ)(LSFN)and La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCo F),LCa FN has a high electrical conductivity (297 S cm^(-1)),TEC compatibility(11.2×10^(-6)K^(-1)) and improved chemical stability.Moreover,LCa FN has high oxygen reduction reaction(ORR)activity with a low polarization resistance(0.06Ωcm^(2)) at 800℃.A single-cell NiYSZ/YSZ/gadolinium-doped ceria(GDC)/LCa FN-GDC operated at 800℃ yields a maximum power density of 1.08 W cm^(-2) using H_(2) as fuel.In the solid oxide electrolysis cell(SOEC)mode,the cell can achieve a current density of approximately 1.2 A cm^(-2) at 1.3 V with 70% humidity at 800℃.The cell exhibits good reversibility and remains stable in continuous SOEC and solid oxide fuel cell(SOFC)modes.These findings indicate the potential application of LCa FN as an air electrode material for RSOCs.

1,3-Dimethyl-2-imidazolidinone: an ideal electrolyte solvent for high-performance Li–O;battery with pretreated Li anode

Electrolytes are widely considered as a key component in Li–O;batteries (LOBs) because they greatly affect the discharge-charge reaction kinetics and reversibility.Herein,we report that 1,3-dimethyl-2-imidazolidinone (DMI) is an excellent electrolyte solvent for LOBs.Comparing with conventional ether and sulfone based electrolytes,it has higher Li_(2)O_(2)and Li_(2)CO_(3)solubility,which on the one hand depresses cathode passivation during discharge,and on the other hand promotes the liquid-phase redox shuttling during charge,and consequently lowers the overpotential and improves the cyclability of the battery.However,despite the many advantages at the cathode side,DMI is not stable with bare Li anode.Thus,we have developed a pretreatment method to grow a protective artificial solid-state electrolyte interface(SEI) to prevent the unfavorable side-reactions on Li.The SEI film was formed via the reaction between fluorine-rich organic reagents and Li metal.It is composed of highly Li^(+)-conducting Li_(x)BO_(y),LiF,Li_(x)NO_(y),Li_(3)N particles and some organic compounds,in which Li_(x)BO_(y)serves as a binder to enhance its mechanical strength.With the protective SEI,the coulombic efficiency of Li plating/stripping in DMI electrolyte increased from 20%to 98.5%and the fixed capacity cycle life of the assembled LOB was elongated to205 rounds,which was almost fivefold of the cycle life in dimethyl sulfoxide (DMSO) or tetraglyme(TEGDME) based electrolytes.Our work demonstrates that molecular polarity and ionic solvation structure are the primary issues to be considered when designing high performance Li–O;battery electrolytes,and cross-linked artificial SEI is effective in improving the anodic stability.

First principles study on methane reforming over Ni/TiO2（110） surface in solid oxide fuel cells under dry and wet atmospheres

Understanding the carbon-tolerant mechanisms from a microscopic view is of special importance to develop proper anodes for solid oxide fuel cells.In this work,we employed density-functional theory calculations to study the CH4 reaction mechanism over a Ni/TiO2 nanostructure,which experimentally demonstrated good carbon tolerance.Six potential pathways for methane reforming reactions were studied over the Ni/TiO2(110)surface under both dry and wet atmospheres,and the main concerns were focused on the impact of TiO2 and Ni/TiO2 interface on CO/H2 formation.Our calculations suggest that the reaction between carbon and the interfacial lattice oxygen to form CO*is the dominant pathway for CH4 reforming under both dry and wet atmospheres,and intervention of steam directly to oxidize C*with its dissociated OH*group is less favorable in energy than that to wipe off oxygen vacancy to get ready for next C*oxidation.In all investigated paths,desorption of CO*is one of the most difficult steps.Fortunately,CO*desorption can be greatly promoted by the large heat released from the previous CO*formation process under wet atmosphere.H2O adsorption and dissociation over the TiO2 surface are found to be much easier than those over Ni,yttria stabilized zirconia(YSZ)and CeO2,which should be the key reason for the greatly depressed carbon deposition over Ni-TiO2 particles than traditional YSZ-Ni and CeO2-Ni anode.Our study presents the detailed CO*formation mechanism in CH4 reforming process over the Ni/TiO2 surface,which will benefit future research for exploring new carbon-tolerant solid oxide fuel cell anodes.

Fabrication and characterization of Ba Ce_(0.8)Y_(0.2)O_(2.9)-Ce_(0.85)Sm_(0.15)O_(1.925) composite electrolytes for IT-SOFCs

The Ba Ce0.8Y0.2O2.9-Ce0.85Sm0.15O1.925 composite electrolytes were prepared with Ba Ce0.8Y0.2O2.9(BCY) and Ce0.85Sm0.15O1.925(SDC). The SDC and BCY powders were mixed in the weight ratio of 95:5, 85:15, and 75:25, respectively(named as BS95, BS85, and BS75). Because of the composite effect between the SDC and BCY phases, the BS95 and BS85 exhibit improved conductivity compared with the pure SDC and BCY. The conductivity of BS95 is higher than that of BS85, indicating that the composite effect of BS95 is greater than that of BS85. Nevertheless, the composite effect in BS75 does not exist. Hence, we conclude that the composite effect in the BCY-SDC composites will decrease with the increase of the amount of BCY and even disappear when the amount of BCY exceeds a certain value. In our case, the optimum composition of the composite electrolyte is 95 wt% SDC and 5 wt% BCY. The BS95 has the highest conductivity(σ1t=0.07808 S cm-1, at 800 °C) and the fuel cell based on the BS95 shows the best performance(the maximum power density reaches as high as 526 mw cm-2 at 750 °C). The encouraging results suggest that the BCY-SDC composites are the very promising electrolyte materials for IT-SOFCs.