Synthesis of amorphous SeP2/C composite by plasma assisted ball milling for high-performance anode materials of lithium and sodium-ion batteries

To promote substantially the performances of red phosphorous (P) anode for lithium and sodium-ion batteries, a simple plasma assisted milling (P-milling) method was used to in-situ synthesize SeP₂/C composite. The results showed that the amorphous SeP₂/C composite exhibits the excellent lithium and sodium storage performances duo to the small nano-granules size and complete combination of selenium (Se) and phosphorous (P) to generate Se–P alloy phase. It was observed that inside the granules of SeP₂/C composite the nanometer size of the SeP₂ particles ensured the fast kinetics for Li⁺ and Na⁺ ​transfer, and the amorphous carbon wrapping the SeP₂ particles relieved volume expansion during lithium/sodium storage processes and enhances electric conductivity. Therefore, the SeP₂/C electrode retained reversible capacities of 700 ​mA ​h ​g⁻¹ at 2 ​A ​g⁻¹ after 500 cycles and 400 ​mA ​h ​g⁻¹ at 0.5 ​A ​g⁻¹ after 400 cycles as anode for LIBs and SIBs, respectively. The result proves that the amorphous SeP₂/C composite can be a new type of anode material with great potential for lithium and sodium-ion batteries.     

膨胀石墨/酚醛树脂复合材料双极板研究

以膨胀石墨为导电骨料、炭黑为添加剂、酚醛树脂为黏结剂,采用模压成形工艺制备质子交换膜燃料电池用膨胀石墨/酚醛树脂复合材料双极板.考察树脂含量、成形压力、添加剂用量及添加剂加入方式对复合材料双极板性能的影响.研究结果表明:上述因素对复合材料双极板的性能影响较大,黏结剂的加入量(质量分数)为20％-30％、压力在10～12 MPa较为合适;炭黑对复合材料双极板的性能影响比较复杂,在实验用炭黑范围内,随着炭黑用量的增加,电导率增大较快,抗折强度先增大后减小;在复合材料的混料过程中,将炭黑添加在树脂中,制备的复合材料双极板性能比炭黑添加在膨胀石墨性能好.     

FeCo-based mesoporous carbon shells modified N-doped porous carbon spheres for oxygen reduction reaction

FeCo-based non-noble metal electrocatalysts (NNMEs) of FeCo/MCS-NPCS was fabricated by immobilization of hemin on mesoporous carbon shells modified N-doped porous carbon spheres (MCS-NPCS). The obtained FeCo/MCS-NPCS exhibits a half-wave potential (E_1/2) of 0.851 ​V versus the reversible hydrogen electrode (vs. RHE) and a limited-diffusion current density (J_L) of 5.45 ​mA ​cm⁻². In addition, FeCo/MCS-NPCS shows comparable oxygen reduction reaction (ORR) performances to 20 ​wt% Pt/C in terms of E_1/2 and J_L and better electrochemical properties, including the methanol tolerance and durability in alkaline solution. Such outstanding electrochemical activities of FeCo/MCS-NPCS can be ascribed to Fe and/or Co-based nitrides and carbides as well as N-doped carbon matrixes modified with mesoporous carbon shells. This research introduces a promising path to design and synthesize highly efficient FeCo–N–C electrocatalysts towards ORR.     

Fenton试剂pH值对碳纳米管及其增强酚醛树脂/石墨复合材料性能的影响

以经过Fenton/UV处理的碳纳米管作为增强体,酚醛树脂/石墨作为基体,通过热模压成型得到一种质子交换膜燃料电池双极板材料.研究了Fenton试剂预处理前pH值对碳纳米管及其增强的复合材料性能的影响.用红外光谱分析碳纳米管表面官能团的变化,用X射线衍射(XRD)对碳纳米管进行物相分析.结果表明,pH值为3时,碳纳米管...     

Graphite-polypyrrole coated 316L stainless steel as bipolar plates for proton exchange membrane fuel cells

316L stainless steel (SS 316L) is quite attractive as bipolar plates in proton exchange membrane fuel cells (PEMFC). In this study, graphite-polypyrrole was coated on SS 316L by the method of cyclic voltammetry. The surface morphology and chemical composition of the graphite-polypyrrole composite coating were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). A simulated working environment of PEMFC was applied for testing the corrosion properties of graphite-polypyrrole coated SS 316L. The current densities in the simulated PEMFC anode and cathode conditions are around 3×10-9 and 9×10-5 A·cm-2, respectively. In addition, the interfacial contact resistance (ICR) was also investigated. The ICR value of graphite-polypyrrole coated SS 316L is much lower than that of bare SS 316L. Therefore, graphite-polypyrrole coated SS 316L indicates a great potential for the application in PEMFC.     

Corrosion resistance and thermal stability of sputtered Fe44Al34Ti7N15 and Al61Ti11N28 thin films for prospective application in oil and gas industry

Fe-and Al-based thin-film metallic glass coatings (Fe₄₄Al₃₄Ti₇N₁₅ and Al₆₁Ti₁₁N₂₈) were fabricated using magnetron co-sputtering technique, and their corrosion performances compared against wrought 316L stainless steel. The results of GI-XRD and XPS analyses demonstrated amorphous structure and oxide layer formation on the surface of the fabricated thin films, respectively. The potentiodynamic (PD) polarization test in chloride-thiosulfate (NH₄Cl ​+ ​Na₂S₂O₃) solution revealed lower corrosion current (I_corr) (0.42 ​± ​0.02 ​μA/cm² and 0.086 ​± ​0.001 ​μA/cm² Vs. 0.76 ​± ​0.05 ​μA/cm²), lower passivation current (I_pass) (1.45 ​± ​0.03 ​μA/cm² and 1.83 ​± ​0.07 ​μA/cm² Vs. 1.98 ​± ​0.04 ​μA/cm²), and approximately six-fold higher breakdown potential (E_bd) for Fe- and Al-based coatings than those of wrought 316L stainless steel. Electrochemical Impedance Spectroscopy (EIS) of both films showed 4- and 2-fold higher charge transfer resistance (R_ct), 7- and 2.5-times higher film resistance (R_f), lower film capacitance values (Q_f) (10 ​± ​2.4 ​μS-s^acm^-2, and 5.41 ​± ​0.8 ​μS-s^acm^-2 Vs. 18 ​± ​2.21 ​μS-s^acm^-2), and lower double-layer capacitance values (Q_dl) (31.33 ​± ​4.74 ​μS-s^acm^-2, and 15.3 ​± ​0.48 ​μS-s^acm^-2 Vs. 43 ​± ​4.23 ​μS-s^acm^-2), indicating higher corrosion resistance of the thin films. Cyclic Voltammetry (CV) scan exhibited that the passive films formed on the Fe- and Al-based coatings were more stable and less prone to pitting corrosion than the wrought 316L stainless steel. The surface morphology of both films via SEM endorsed the CV scan results, showing better resistance to pitting corrosion. Furthermore, the thermal analysis via TGA and DSC revealed the excellent thermal stability of the thin films over a wide temperature range typically observed in oil-gas industries.     

ZIF-derived Co–N–C ORR catalyst with high performance in proton exchange membrane fuel cells

Metal and nitrogen-doped carbon (M-N-C) materials have been considered as the most promising non-precious metal oxygen reduction (ORR) catalysts to replace expensive Pt catalysts. Due to high Fenton catalytic activity of Fe element and the resulting instability, Co-based N–C (Co–N–C) catalysts without Fenton catalytic activity should be a worthier ORR catalyst being explored. Although the high ORR activity of Co–N–C catalyst has been demonstrated in aqueous half-cell tests, their performance under PEMFC working condition is still far away from that of state-of-the-art Fe–N–C catalysts. In this study, a high-performance Co–N–C catalyst was synthesized by one-step pyrolyzing Co-doped ZIF-8 (zeolitic imidazolate framework-8) particles in-situ grown on the high-surface-area KJ600 carbon black with high electronic conductivity. The resulting Co–N–C catalyst exhibited high intrinsic ORR activity, fast mass transfer rate and high electronic conductivity, and thus yielded a remarkable peak power density of 0.92 W cm^-2 in H₂–O₂ PEMFC, which is comparable to state-of-the-art Fe–N–C catalyst. This strategy is helpful to synthesize highly active M-N-C ORR catalysts with improved mass transfer and electric conductivity.     

Flexible free-standing polyaniline/poly(vinyl alcohol) composite electrode with good capacitance performance and shape memory behavior

The increasing demand for portable and flexible energy storage devices drives the development of flexible electrodes and electrolytes. The aim of this work is to fabricate the flexible free-standing polyaniline/poly (vinyl alcohol) (PANI/PVA) composite electrode with good capacitance performance and shape memory behavior. The electrodes were fabricated by chemical oxidation polymerization of aniline in porous PVA (P-PVA) films. The morphology, electrochemical and mechanical properties of PANI/P-PVA electrodes were studied by scanning electron microscope, cyclic voltammetry, galvanostatic charge-discharge, and tensile test etc. The results revealed that the flexible PANI/P-PVA-1 electrode had good specific capacitance of 173.86 ​mF ​cm⁻² at 1 ​mA ​cm⁻², with the capacitance retention of 70.16% after 4000 charge-discharge cycles. Besides, it had excellent heat-induced shape memory effect. The fixed shape could completely recover to its original shape within 10 ​s at 80 ​°C, which is above the glass transition temperature (75.89 ​°C) of PANI/P-PVA-1. The comparatively tensile strength (2.86 ​MPa) and high elongation at break (315.72%) indicated its outstanding flexibility. Up to 200 times folding had no effect on the electrochemical properties. The free-standing polymer electrodes with excellent comprehensive performance provide potential applications in flexible energy-storage devices, electronic encapsulation and high stretchable electric devices etc.     

质子交换膜燃料电池薄金属双极板性能优化与设计

针对质子交换膜燃料电池制造技术实用化的瓶颈，研究了质子交换膜燃料电池低成本制造与性能优化问题，建立了质子交换膜燃料电池半个单池的三维计算模型，采用计算流体动力学技术对阳极燃料气体（H2）流场进行了数值模拟；以阳极最大燃料气体（H2）利用率为目标优化流场板沟槽尺寸，设计了一种操作成本低、容易批量生产的板料冲压成形薄金属双极板结构，可增大电池组体积比功率和提高燃料电池的性能；利用弹塑性有限元方法模拟阳极流场板冲压成形过程，验证了板料冲压成形金属双极板结构的可行性．     

Spectroscopic properties of Er3+/Ho3+/Tm3+ doped α-SiAlON ceramics under 793 ​nm excitation

This paper reports the first demonstration of super broadband infrared downshifting emission extending from 1640 ​nm to 2200 ​nm with the full width at half maximum of ∼ 417 ​nm in lanthanides (Er³⁺, Ho³⁺, and Tm³⁺)-doped α-SiAlON ceramics upon 793 ​nm excitation. Using α-Si₃N₄ ceramic as a precursor the lanthanides-doped α-SiAlON ceramics were synthesized by the hot-press method. The lanthanides induced no significant secondary phases in the sintered α-SiAlON ceramics. Strong two-photon upconversion emission bands centered at 547, 671 and 694 ​nm have also been observed upon 793 ​nm excitation. The time-resolved measurements of the upconversion emissions confirm that the efficient energy transfer among the Er³⁺, Ho³⁺ and Tm³⁺ ions as well as the ground state absorption in Er³⁺ and Tm³⁺ are responsible for the observed spectroscopic properties.     

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.     

质子交换膜燃料电池金属双极板表面改性涂层研究进展

用于质子交换膜燃料电池(PEMFC)的金属双极板,因其可加工性强、导热导电性优而受到广泛关注．作为燃料电池的重要组成部分,双极板的生产成本和性能是电堆投入实际应用、扩大应用范围的关键．金属双极板在PEMFC酸性且润湿的环境中,受到的侵蚀及其表面氧化带来的接触电阻的降低对其实际应用产生了挑战．本文简述了制备双极板表面改性涂层的方法,对比了用于极板改性的多类型涂层(金属基涂层、非晶碳涂层和氮化物涂层)在膜基结合力、界面导电性、耐腐蚀性能和疏水性等方面的差别,分析了改性涂层的腐蚀机制和影响涂层性能表现的因素,探讨了涂层在结构设计、失效机制、元素选择等方面存在的问题,讨论了降低极板成本、提高耐久性这一极板改性研究的主要趋势．      

Current Research Progress in Magnesium Borohydride for Hydrogen Storage (A review)

Hydrogen storage in solid-state materials is believed to be a most promising hydrogen-storage technology for high efficiency, low risk and low cost. Mg(BH₄)₂ is regarded as one of most potential materials in hydrogen storage areas in view of its high hydrogen capacities (14.9 ​wt% and 145–147 ​kg ​cm⁻³). However, the drawbacks of Mg(BH₄)₂ including high desorption temperatures (about 250 ​°C–580 ​°C), sluggish kinetics, and poor reversibility make it difficult to be used for onboard hydrogen storage of fuel cell vehicles. A lot of researches on improving the dehydrogenation reaction thermodynamics and kinetics have been done, mainly including: additives or catalysts doping, nanoconfining Mg(BH₄)₂ in nanoporous hosts, forming reactive hydrides systems, multi-cation/anion composites or other derivatives of Mg(BH₄)₂. Some favorable results have been obtained. This review provides an overview of current research progress in magnesium borohydride, including: synthesis methods, crystal structures, decomposition behaviors, as well as emphasized performance improvements for hydrogen storage.     

增强金属基双极板导电和耐腐蚀性能的石墨烯基涂层的研究进展

应用于金属基双极板的石墨烯基涂层引起人们广泛的兴趣。综述了目前金属基双极板面临的问题,总结了已经报道的关于制备石墨烯基涂层的方法（化学气相沉积法、电沉积法、喷涂法、自组装方法）以及这些方法的优缺点。石墨烯优良的阻隔性能可以充当金属基双极板的钝化膜,对石墨烯进行改性或者对金属基双极板进行表面处理可以有效地改善石墨烯涂层与金属基双极板的相容性。导电聚合物可以有效地改善石墨烯涂层与金属基之相容性,并且能够填补石墨烯片层间的缝隙,提高涂层的致密度。导电聚合物能够以石墨烯为模板进行生长,降低涂层的表面粗糙度。最后提出对石墨烯改性以增强其与金属基双极板的相容性,以及发挥其与导电聚合物协同效应是未来的研究方向之一。     

Conductive and corrosion behaviors of silver-doped carbon-coated stainless steel as PEMFC bipolar plates

Ni–Cr enrichment on stainless steel SS316L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316L substrate. The corrosion resistance of this film in 0.5 mol·L-1 H₂SO₄ solution containing 5 ppm F- at 80℃ was investigated using polarization tests. The results showed that the surface treatment of the SS316L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316L, the Ag-doped carbon-coated SS316L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell (PEMFC) and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 mΩ·cm2 to 21.6 mΩ·cm2 at a compaction pressure of 1.2 MPa.     

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)Fe₂O₄spinel oxide(M-(Ni, Zn)Fe₂O₄). Results indicated the magnetic field(≤250 m T) would affect the morphology of catalyst due to the existing Fe ions, inducing the M-(...     

Rational design of MnS nanoparticles anchored on N,S-codoped carbon matrix as anode for lithium-ion batteries

The manganese sulfide (MnS) has attracted more attention as anode material on energy storage and conversion field, owing to its high theoretical capacity (616 ​mA ​h ​g⁻¹) and good electrochemical activity. However, low electronic conductivity and large volume expansion during charge-discharge processes have limited its further application. In order to address above mentioned problems, the composites, MnS nanoparticles embedded in N,S-codoped porous carbon skeleton (named as MnS/N,S–C composites), herein have been prepared successfully using metal organic framework (Mn-NTA) as template. The porous carbon skeleton not only can enhance electrode conductivity, but also relieve volume expansion during charge-discharge processes. Thus, the rational design towards electrode architectures has endowed MnS/N,S–C nanocomposites with superior electrochemical performance, which delivers the specific capacities of 676.7 ​mA ​h ​g⁻¹ at the current density of 100 ​mA ​g⁻¹.     

细鳞片膨胀石墨在燃料电池中的应用分析

本文简述了质子交换膜燃料电池双极板的基本概念,分析了细鳞片膨胀石墨在质子交换膜燃料电池中应用的优缺点。指出细鳞片膨胀石墨优点是比表面积大、密度均匀、复合性能好,不足之处在于纯度不够高,在回弹性、导电性方面不如大鳞片膨胀石墨。指出细鳞片膨胀石墨在质子交换膜燃料电池中的应用发展方向在于复合双极板。     

Thermal damage and ablation behavior of plasma sprayed Ba2SmTaO6 coatings irradiated by high power continuous laser

Ba₂SmTaO₆ laser protection coatings of ≈200 ​μm thickness were deposited onto stainless steel surfaces by air plasma spraying, and the laser irradiation resistance of the coatings was investigated. For laser irradiation with a laser power density less than 1000 ​W/cm², the coatings kept intact. For a laser power density exceeding 1500 ​W/cm², the Ba₂SmTaO₆ coatings underwent recrystallization, grain growth occurred, and certain spray morphology features disappeared by melting. In the case of a laser power density of 2000 ​W/cm² applied for 10s, the incident laser parameter was beyond the coatings protection threshold, and the coating peeled off. The samples back surface temperature kept unchanged within the first 1s of laser irradiation, indicating that Ba₂SmTaO₆ coatings have excellent laser protection capability and can limit the rise of the substrate temperature. However, the low thermal conductivity of Ba₂SmTaO₆ leads to a detrimental laser energy concentration at the beginning of the laser irradiation period on the sample front surface, resulting in a rapid increase of the surface temperature up to the melting point.     

Large specific surface area S-doped Fe–N–C electrocatalysts derived from Metal–Organic frameworks for oxygen reduction reaction

It is highly desired but challenging to develop platinum group metal-free electrocatalysts for oxygen reduction reaction (ORR), which can promote the commercialization of fuel cell technology. To achieve this target, we report a one-step doping method to prepare S-doped Fe–N–C catalysts using zeolite imidazole framework (ZIF-8) and iron (III) thiocyanate (Fe(SCN)₃) as precursor. Different from conventional doping approach, i.e. physical mixing, Fe(SCN)₃ is in-situ added during ZIF-8 formation which would encapsulate Fe(SCN)₃ molecules inside ZIF-8 to avoid structure destruction and create potential replacement of Zn ions by Fe ions to form uniform Fe–N₄ complexes. As a result, the prepared S-doped Fe–N–C catalysts own large specific surface areas with a maximum value of 1326 ​m² ​g⁻¹ and a dual-scale porous structure that benefits mass transport. Significantly, the composition-optimized catalyst exhibits superior ORR activity in both 0.1 ​M HClO₄ electrolyte and 0.1 ​M KOH electrolyte, in which the half-wave potential reaches 0.81 ​V and 0.92 ​V (vs. RHE), respectively. Remarkable stability is also attained, which loses 2 ​mV only after 10000 potential cycles in O₂-saturated 0.1 ​M HClO₄ and remains almost constant in O₂-saturated 0.1 ​M KOH, surpassing commercial Pt/C catalyst in both acidic and alkaline medium.