Nickel-introduced structurally ordered PtCuNi/C as high performance electrocatalyst for oxygen reduction reaction

Designing highly active and durable oxygen reduction reaction (ORR) electrocatalysts is essential for developing efficient proton-exchange membrane fuel cells (PEMFCs). In this work, ordered PtCuNi/C nanoparticles (NPs) were synthesized using an impregnation reduction method. This study shows that the incorporation of Ni in ordered PtCu/C can effectively adjust the electronic structure of Pt, thereby optimizing oxygen binding energy for the ORR. The obtained intermetallic ordered PtCuNi/C NPs significantly improved ORR activity and durability compared to ordered PtCu/C. Specifically, PtCu_0·5Ni_0·5/C-700 shows a mass activity of 1.29 ​A ​mg _Pt⁻¹ ​at 0.9 ​V vs. reversible hydrogen electrode (RHE), which is about 9.2 times higher than that of commercial Pt/C. PtCu_0.5Ni_0.5/C-700 is also shown to be competent cathode catalyst for a single-cell system exhibiting high power density (461 ​mW ​cm⁻²). This work demonstrates that ordered PtCu_0·5Ni_0·5/C-700 can be used as a highly active and durable ORR catalyst in PEMFCs.     

Effect of polytetrafluoroethylene (PTFE) in current collecting layer on the performance of zinc-air battery

Beyond reasonable designing catalysts, the optimization of preparing air cathode has far-reaching implications for the development of Zinc-air batteries. In this study, the effect of Polytetrafluoroethylene (PTFE) in current collecting layer on the performance of Zinc-air battery was investigated. The results showed that as the polytetrafluoroethylene (PTFE) content and heat treatment temperature changed, the hydrophobicity and porosity of current collecting layer also changed, thereby affecting the performance of air cathode. The air cathode assembled with PTFE-3-300 possessed an excellent electrochemical performance, which was prepared by brushing PTFE and acetylene black (wherein the mass ratio of them is 18:5) on current collecting layer and then heating at 300 °C. The obtained air cathode displayed relatively small polarization loss and excellent rate performance, showing a polarization potential of - 0.405 V vs. Hg/HgO at 100 mA cm⁻² and the voltage retention of 94.47% from 5 to 20 mA cm⁻². Besides, the air cathode displayed excellent discharge stability maintaining average potential 1.3249 V for 100 h. Based on this work, a detailed understanding of the relationship of PTFE and current collecting layer can be achieved to improve the electrode design, architecture and fabrication.     

Laboratory study of improving petroleum recovery by changing the wettability between the solid/liquid interface

The wettability of the solid powders (silica gel or Kaolin) was measured with the modified Washburn equation indicated as contact angles. The wettability changes for SDBS aqueous solutions on the surface of a silica gel or Kaolin powder were studied. The average aggregation number of the micelle in SDBS aqueous solution was measured by the fluorescence quenching method. Then the oil recovery of n-dodecane on the silica gel or the Kaolin surface was tested. The relationship between the wettability of the powder surface, the critical micelle concentration (CMC) of SDBS aqueous solution, and the mimic oil recovery of the resident oil on the powder surface has been explored. It has been found that the minimum contact angle (most hydrophilic condition) and the maximum oil recovery occurred near the critical micelle concentration (CMC) of SDBS while the interfacial tension between the SDBS solution and n-dodecane was far from ultra-low condition (≤10^-3 mN·m^-1).     

Li3N film modified separator with homogenization effect of lithium ions for stable lithium metal battery

Lithium metal anode with high theoretical capacity is considered to be one of the most potential anode materials of the next generation. However, the growth of lithium dendrite seriously affects the application of lithium metal anode and the development of lithium metal batteries (LMBs). Herein, an ultrathin Li₃N film modified separator to homogenize the lithium ions and protect the lithium metal anode was reported. Due to the intrinsic properties of Li₃N, the functional separator possessed good thermal stability, mechanical properties and electrolyte wettability, and the homogenization of the lithium ion was realized without increasing the interface impedance. With this functional separator, the Li/Li symmetrical cell could achieve a long cycle with low overpotential for 1000 ​h at a current density of 1 ​mA ​cm⁻². Furthermore, when the full battery was assembled with LiFePO₄ and the discharge capacity could be maintained at 151 mAh g⁻¹ after 400 cycles at 1 ​C. In addition, the full battery also showed good rate performance, and provided a high discharge capacity of 114 mAh g⁻¹ at 5 ​C.     

Gas-Liquid Interfacial Plasma engineering under dilute nitric acid to improve hydrophilicity and OER performance of nickel foam

The world has been moving rapidly to find new eco-friendly energy sources. Water electrolysis consists of two reactions of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), whereas the OER is considered the rate-limiting step. The most commercialized electrode for OER in the alkaline electrolyte is Ni foam, but its original surface is hydrophobic. It is possible to accelerate the adsorption and desorption process of reactants and products during OER by adding hydrophilic functional groups such as –OH on the surface of Ni foam. In this study, a novel Gas-Liquid Interfacial Plasma (GLIP) engineering at room temperature was successfully applied to modify the Ni foam surface dilute (1 ?M) HNO₃ solution. At a current density of 400 ?mA ?cm^?2, GLIP-treated Ni foam electrodes at 1 ?M HNO₃ concentrations showed OER overpotentials of 458 ?mV. Among all, GLIP with 1 ?M HNO₃ treatment of 30 ?min showed 129 ?mV less overpotential than the nickel foam before treatment. In summary, GLIP can be justified as an environmentally friendly and efficient surface treatment to improve the wettability and OER performance of Ni-based electrodes in water electrolysis.     

Pyrolysis of Iron(III) porphyrin coated Pt/C toward oxygen reduction reaction in acidic medium

Design and synthesis of highly active and durable electrocatalysts toward oxygen reduction reaction (ORR) is of particular importance for proton exchange membrane fuel cells (PEMFCs), yet remains a grand challenge. Herein, we report the deposition of iron (III) porphyrin (FeP) on house-made Pt/C by rotary evaporation of the mixture of FeP and house-made Pt/C dispersed in chloroform, followed by pyrolysis at 650 °C in argon atmosphere. This approach led to the synthesis of new non-precious metal electrocatalyst (NPME)-Pt/C composites (Pt/C–FeP) with an average nanoparticle diameter of 3.1 ± 1.5 nm without aggregation. According to X-ray photoelectron spectroscopy (XPS), the binding energy of Pt 4f_7/2 became larger due to the presence of pyrolyzed FeP. In addition, the electrochemically active surface area (ECSA) of Pt/C–FeP-650 is 65 m²/g less than that of house-made Pt/C (80.2 m²/g). This implies that the pyrolyzed FeP may have partially covered the surface of Pt nanoparticles and thus lowering the ECSA. Interestingly, the mass activity (MA) of Pt/C–FeP turns out to be 349.0 mA/mg_Pt @0.9 V vs. RHE, which is 2.6 times and 1.5 times of house-made Pt/C and commercial Pt/C, respectively. It is speculated that the electronic interaction and possible synergy between Pt and pyrolyzed FeP as NPME might have contributed to the ORR activity improvement despite of partial loss of ECSA. During accelerated durability tests (ADTs), the MA of Pt/C–FeP-650 degrades 64.3% inferior to commercial Pt/C (52.2%). The main reason likely arises from the degradation of pyrolyzed FeP, which is a bottleneck problem confronting NPMEs.     

冰晶石-氧化铝熔体对铂电极的湿润

采用无壁电解槽研究了铝电解质对铂电极的湿润性,报道了熔滴沿铂阴极向上蠕动,电解质在碳极上的铺展与收敛、阳极效应时电解质在铂阴极上打“秋千”等现象,推导并依据在极化条件下的杨氏(T.Young)方程,认为上述现象是缘于双电层中同性电荷相斥所致。     

Enhanced low-humidity performance of proton-exchange membrane fuel cell by introducing hydrophilic CNTs in membrane electrode assembly

Hydrophilic carbon nanotubes (HCNTs) were introduced into the membrane electrode assembly (MEA) to improve its low-humidity performance. The effects of types, placement, loading, and relative humidity on the MEA performance were investigated. It has been found that the MEA with 20 ?wt% HCNTs loading both in anode and cathode achieved the best self-humidifying performance. Its current density reached 1550 ?mA ?cm^?2 at 0.6 ?V, with a maximum power density of 953 ?mW/cm² at 70 ?°C, 30 psi and 30% relative humidity conditions. Besides, the stability test shows that its current density at 0.6 ?V only decreased by 6.4% after 44 ?h performance test, while the performance of blank MEA without HCNTs decreased by 45% within 6 ?h testing period. This extraordinary performance under low humidity condition is ascribed to that the HCNTs contained in the MEA improve the water management and mass transportation by functioning as a dispersant and hydrophilic agent.     

Microstructure and mechanical properties of TiAl/TiAl joints brazed with a newly developed Ti–Ni–Nb–Zr quaternary filler alloy

A novel Ti–Ni–Nb–Zr quaternary filler alloy with the composition of Ti-(19～25)Ni-(15～25)(Nb ?+ ?Zr) (wt.%) was designed. The filler alloy was composed of (Ti,Nb)ss, (Ti,Zr,Nb)ss ?+ ?(Ti,Zr)₂Ni, α-Ti and Ti₂Ni phases. It was fabricated into filler foil with a thickness of about 45 ?μm by a rapid solidification technique. The results indicate that the liquidus temperature of the Ti–Ni–Nb–Zr brazing alloy was about 978 ^oC, and the brazing alloy presented excellent wettability on TiAl substrate. The TiAl joint mainly consisted of β/B2 phase, Ti₂Al, Ti₂AlNi and α₂-Ti₃Al phases. The diffusion of Al atom from base metal to brazed seam led to the formation of Ti₂Al and Ti₂AlNi. Considering that no previously references on XRD pattern of Ti₂AlNi compound can be found, Ti₂AlNi cast alloy specimen was specially prepared and XRD peaks were specially labeled. The micro-hardness and bending strength tests of the Ti₂AlNi phase were carried out, and the results were 761 HV and 192 ?MPa, respectively. The brazing parameters of 1010 ^oC/10 ?min offered the joint shear strength of 280 ?MPa at room temperature, and the joints exhibited tensile strength of 372 ?MPa at room temperature and 340 ?MPa at 750 ^oC, indicating that the newly developed filler alloy could offer a stable high-temperature strength.     

Magnetic field induced synthesis of (Ni,Zn)Fe2O4 spinel nanorod for enhanced alkaline hydrogen evolution reaction

Recently, the introduction of external fields (light, thermal, magnetism, etc.) during electrocatalysis reactions gradually becomes a new strategy to modulate the catalytic activities. In this work, an external magnetic field was innovatively employed for the synthesis progress of (Ni, Zn)Fe₂O₄ spinel oxide (M-(Ni, Zn)Fe₂O₄). Results indicated the magnetic field (≤250 ​mT) would affect the morphology of catalyst due to the existing Fe ions, inducing the M-(Ni, Zn)Fe₂O₄ nanosphere particles to be uniform and coral-like nanorods. In addition, the electronic structure of the catalyst was regulated by the valence state of Fe, changing the bonding of metal to oxygen atoms in different spinel sites. The results manifested that the M-(Ni, Zn)Fe₂O₄ requires a lower overpotential of only 67 ​mV to deliver 10 ​mA ​cm⁻² for hydrogen evolution reaction (HER) in alkaline electrolyte. Moreover, M-(Ni, Zn)Fe₂O₄ respectively as the anode and cathode electrode for the overall water splitting, the catalysis system requires a cell voltage of only 1.76 ​V to gain a current density of 50 ​mA ​cm⁻², combining with an excellent discharging stability after 10 ​h. This work provides a facile synthesis strategy toward the design of efficient non-noble metal catalysts for alkaline HER and overall water splitting.     

质子交换膜燃料电池三维气液两相流数值模拟

质子交换膜燃料电池液态水的生成和传输过程研究,是进行电池水管理的关键。该文基于多相混合流理论,建立了质子交换膜燃料电池三维气液两相流动与传热的数学模型。该模型不仅能模拟燃料电池内部反应气的流动、扩散和化学反应过程,还能模拟液态水的传输和相变过程。应用该模型模拟了电池内液态水的分布及其对燃料电池性能的影响,结果表明液态水主要分布在阴极侧,在大电流密度下,液态水阻碍了氧的扩散过程,导致电池性能下降。模拟结果与实验结果吻合较好。     

Effect of La0.8Sr0.2Co0.2Fe0.8O3-δ morphology on the performance of composite cathodes

In the present work,one dimensional La0.8Sr0.2Co0.2Fe0.8O3 δ(LSCF) nanofibers with the mean diameter of about 100 nm prepared by electrospinning were deposited on Gd0.2Ce0.8O1.9(GDC) electrolyte followed by sintering to form one dimensional LSCF nanofiber cathode. And LSCF/GDC composite cathodes were formed by introducing GDC phases into LSCF nanofiber scaffold using infiltration method. The polarization resistances for the composite cathode with an optimal LSCF/GDC mass ratio of 1/0.56 are 0.27,0.14 and 0.07 Ω cm2at 650,700 and750 1C,respectively,which are obviously smaller than 2.26,0.78 and 0.29 Ω cm2of pure LSCF nanofiber cathode. And the activation energy is1.194 eV,which is much lower than that of pure LSCF nanofiber cathode(1.684 eV). These results demonstrate that the infiltration of GDC into LSCF nanofiber scaffold is an effective approach to achieve high performance cathode for solid oxide fuel cells(SOFCs). In addition,the performance of composite cathode in this work was also compared with that of our previous nanorod structured LSCF/GDC composite cathode.     

熔盐电镀制取铝电解用TiB2惰性阴极

采用熔盐电解法在碳阴极上电镀TiB2铝电解用惰性阴极材料,电解温度800℃,电解质组成(质量分数,%)为KCl4.8,KF55.7,K2TiF615.3,KBF424.2,电流密度为0 3A/cm2,电解3h·对制得的镀层做XRD和EMP电子探针形貌分析,实验结果表明,镀层成分为单一的TiB2,无杂相·镀层厚度可达0.2mm,表面平整,分布均匀,与碳基体结合良好,且有金属光泽·说明该电解条件下,Ti和B能够在阴极上共沉积并生成TiB2·     

质子交换膜燃料电池空气流场的优化设计

质子交换膜燃料电池空气流场的合理设计可以使电流密度、气体浓度等均匀分布,有利于提高性能。采用数值模拟与测试相结合的方法,对5种常见的空气流场进行了综合评价。结果显示,模拟结果与测试结果反映的电池性能变化趋势基本相同,性能由低到高依次为:平行流场、网格流场、平行蛇形流场、渐缩流场。串并联流场的模拟和实验结果略有差异。该方法可用于质子交换膜燃料电池空气流场的优化设计。     

界面特性对聚合物驱油时驱替速度的影响分析

针对界面特性（界面流变特性、界面张力特性、润湿性）在聚合物驱油过程中的重要性,将油藏孔隙介质简化成具有相继收缩和扩张的波纹管模型,根据能量平衡原理建立了波纹管中聚合物溶液驱替时的界面特性参数和驱替速度之间的数学模型,用有限差分方法求解,研究了界面粘度、界面张力、润湿角变化对聚合物/油界面速度的影响。研究结果表明：润湿性变化影响界面的驱替速度,当界面的曲率方向与驱替方向相反时,无因次界面张力和无因次界面粘度的增加都使无因次界面轴向速度降低,且界面轴向驱替速度关于孔隙单元中心不对称。     

锂离子电池正极材料锂钒氧的固相合成

以Li2CO3和V2O5为原料,进行了固相法制备锂离子电池正极材料Li1+xV3O8的实验研究.通过TG-DTA,XRD及交流阻抗等测试方法考察了合成条件对Li1+xV3O8样品结构、电导率及电化学性能的影响.XRD结果表明:随着焙烧温度的提高,产物的(100)衍射峰相对强度增强,这使Li+在LiV3O8中嵌入脱出的路径较长.交流阻抗测试表明:随着烧结温度的提高,电导率增大,而随着烧结时间的延长,电导率出现先增大而后又减小的趋势.电化学测试结果表明,580℃焙烧20 h合成的产物具有优良的电化学性能,放电比容量最高达到254.0 mAh.g-1,10次循环后仍保持在245.6 mAh.g-1,...     

Applications of M/N/C analogue catalysts in PEM fuel cells and metal-air/oxygen batteries: Status quo,challenges and perspectives

To meet the sharp increase in demand for clean and renewable energy, it is necessary to develop new energy-conversion and storage technologies, such as proton exchange membrane fuel cells (PEMFCs) and metal-air/oxygen batteries (MABs). Due to the sluggish reaction kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in the cathodes of PEMFCs and MABs, significant amounts of precious metal catalysts need to be used, driving up the cost of fuel cells and MABs and thereby hindering their commercialization on a large scale. Transition metal and nitrogen co-doped carbonaceous catalysts (M/N/C) have high catalytic activity towards the ORR and OER once the catalysts are modified with certain promoters/additives. In addition, M/N/C catalysts can be prepared from abundant, inexpensive materials, making their cost negligible compared with precious metal catalysts, a development that would efficiently decrease the cost of PEMFCs and MABs. In last decade, numerous researchers have attempted to realize these applications of M/N/C catalysts, and some exciting results have been achieved, making these promising replacements for precious metal catalysts. However, some serious problems and significant challenges remain. In this paper, we review the research on the application of M/N/C analogue catalysts in PEMFCs and MABs in the last 10 years, indicate the remaining challenges, and suggest the future research directions.     

An electrochemical impedance spectroscopic study of the electronic and ionic transport properties of LiCoO2 cathode

The storage behavior and process of the first delithiation-lithiation of LiCoO2 cathode were investigated by electrochemical impedance spectroscopy(EIS). The electronic and ionic transport properties of LiCoO2 cathode along with variation of electrode potential were obtained in 1 mol·L?1 LiPF6-EC:DMC:DEC electrolyte solution. It was found that after 9 h storage of the LiCoO2 cathode in electrolyte solu-tions,a new arc appears in the medium frequency range in Nyquist plots of EIS,which increases with increasing the storage time. In the charge/discharge processes,the diameter of the new arc is reversi-bly changed with electrode potential. Such variation coincides well with the electrode potential de-pendence of electronic conductivity of the LiCoO2. Thus this new EIS feature is attributed to the change of electronic conductivity of LixCoO2 during storage of the LiCoO2 cathode in electrolyte solutions,as well as in processes of intercalation-deintercalationtion of lithium ions. It has been revealed that the reversible increase and decrease of the resistance of SEI film in charge-discharge processes can be also ascribed to the variation of electronic conductance of active materials of the LiCoO2 cathode.     

Electrochemical characterization of MnO2 as the cathode material for a high voltage hybrid capacitor

Manganese dioxide (MnO₂) was prepared using the ultrasonic method. Its electrochemical performance was evaluated as the cathode material for a high voltage hybrid capacitor. And the specific capacitance of the MnO₂ electrode reached 240 F·g-1. The new hybrid capacitor was constructed, combining A1/Al₂O₃ as the anode and MnO₂ as the cathode with electrolyte for the aluminum electrolytic capacitor to solve the problem of low working voltage of a supercapacitor unit. The results showed that the hybrid capacitor had a high energy density and the ability of quick charging and discharging according to the electrochemical performance test. The capacitance was 84.4 μF, and the volume and mass energy densities were greatly improved compared to those of the traditional aluminum electrolytic capacitor of 47 μF. The analysis of electrochemical impedance spectroscopy (EIS) showed that the hybrid capacitor had good impedance characteristics.     

Bimetal nickel–cobalt phosphide directly grown on commercial graphite substrate by the one-step electrodeposition as efficient electrocatalytic electrode

It is challenging to find a method to obtain a catalyst with low cost and efficient multifunctional performances. Herein, in order to obtain the electrode with high-performance water splitting and non-enzymatic glucose detection, the commercial graphite sheet (GS) with excellent durability and electroconductivity was used as substrate material, and the non-noble ternary component Ni–Co–P catalyst with hierarchical architecture was fabricated on GS via a co-electrodeposition. The catalyst only required low overpotentials of 44.6, 76.5 and 49 mV to drive the current density of 10 mA cm⁻² alongside with the smaller Tafel slopes of 39.2, 44.8 and 112 mV dec⁻¹ for hydrogen evolution reaction (HER) in 1.0 M KOH, 0.5 M H₂SO₄ and 1.0 M PBS solution, respectively. For oxygen evolution reaction (OER), the catalyst demonstrated a low overpotential of 304 mV to achieve the current density of 20 mA cm⁻² with excellent Tafel slope of 89.8 mV dec⁻¹ in alkaline solution. Furthermore, the Ni–Co–P/GS electrode serving as non-enzymatic glucose sensor exhibited the superior electrocatalytic activity with an ultrahigh sensitivity of 7400 μA mM⁻¹ cm⁻², low detection limit of 0.425 μM (S/N = 3), and wide linear range (1–1200 μM).