首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 49 毫秒
1.
Electrocatalytic water splitting is one of the sustainable and promising strategies to generate hydrogen fuel but still remains a great challenge because of the sluggish anodic oxygen evolution reaction (OER). A very effective approach to dramatically decrease the input cell voltage of water electrolysis is to replace the anodic OER with hydrazine oxidation reaction (HzOR) due to its lower thermodynamic oxidation potential. Therefore, developing the low‐cost and efficient HzOR catalysts, coupled with the cathodic hydrogen evolution reaction (HER), is tremendously important for energy‐saving electrolytic hydrogen production. Herein, a new‐type of copper–nickel nitride (Cu1Ni2‐N) with rich Cu4N/Ni3N interface is rationally constructed on carbon fiber cloth. The 3D electrode exhibits extraordinary HER performance with an overpotential of 71.4 mV at 10 mA cm?2 in 1.0 m KOH, simultaneously delivering an ultralow potential of 0.5 mV at 10 mA cm?2 for HzOR in a 1.0 m KOH/0.5 m hydrazine electrolyte. Moreover, the electrolytic cell utilizing the synthesized Cu1Ni2‐N electrode as both the cathode and anode display a cell voltage of 0.24 V at 10 mA cm?2 with an excellent stability over 75 h. The present work develops the promising copper–nickel‐based nitride as a bifunctional electrocatalyst through hydrazine‐assistance for energy‐saving electrolytic hydrogen production.  相似文献   

2.
Stable and seamless interfaces among solid components in all‐solid‐state batteries (ASSBs) are crucial for high ionic conductivity and high rate performance. This can be achieved by the combination of functional inorganic material and flexible polymer solid electrolyte. In this work, a flexible all‐solid‐state composite electrolyte is synthesized based on oxygen‐vacancy‐rich Ca‐doped CeO2 (Ca–CeO2) nanotube, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and poly(ethylene oxide) (PEO), namely Ca–CeO2/LiTFSI/PEO. Ca–CeO2 nanotubes play a key role in enhancing the ionic conductivity and mechanical strength while the PEO offers flexibility and assures the stable seamless contact between the solid electrolyte and the electrodes in ASSBs. The as‐prepared electrolyte exhibits high ionic conductivity of 1.3 × 10?4 S cm?1 at 60 °C, a high lithium ion transference number of 0.453, and high‐voltage stability. More importantly, various electrochemical characterizations and density functional theory (DFT) calculations reveal that Ca–CeO2 helps dissociate LiTFSI, produce free Li ions, and therefore enhance ionic conductivity. The ASSBs based on the as‐prepared Ca–CeO2/LiTFSI/PEO composite electrolyte deliver high‐rate capability and high‐voltage stability.  相似文献   

3.
Lithium–sulfur batteries (LSBs) are currently considered as promising candidates for next‐generation energy storage technologies. However, their practical application is hindered by the critical issue of the polysulfide‐shuttle. Herein, a metal organic framework (MOF)‐derived solid electrolyte is presented to address it. The MOF solid electrolyte is developed based on a Universitetet i Oslo (UIO) structure. By grafting a lithium sulfonate (‐SO3Li) group to the UIO ligand, both the ionic conductivity and the polysulfide‐suppression capability of the resulting ‐SO3Li grafted UIO (UIOSLi) solid electrolyte are greatly improved. After integrating a Li‐based ionic liquid (Li‐IL), lithium bis(trifluoromethanesulfonyl)imide in 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, the resulting Li‐IL/UIOSLi solid electrolyte exhibits an ionic conductivity of 3.3 × 10?4 S cm?1 at room temperature. Based on its unique structure, the Li‐IL/UIOSLi solid electrolyte effectively restrains the polysulfide shuttle and suppresses lithium dendritic growth. Lithium–sulfur cells with the Li‐IL/UIOSLi solid electrolyte and a Li2S6 catholyte show stable cycling performance that preserves 84% of the initial capacity after 250 cycles with a capacity‐fade rate of 0.06% per cycle.  相似文献   

4.
We have used inelastic laser light scattering to study the kinetics of the spontaneous assembly of heads and tails of bacteriophage T4D to form noninfectious tail fiberless particles. For interpretation of the kinetics, it was first necessary to determine the physical properties of the strongly scattering phage parts. For heads, these are D20,w = 3.60 × 10−8cm2/s, 820,w = 1025 S, M = 1.76 × 108. For tail fiberless particles, D20,w = 3.14 × 10−8cm2/s, 820,w = 968 S, and M = 1.95 × 108. The kinetics of the head-tail joining process was followed by measuring the time variation of the homodyne scattering autocorrelation function. This was interpreted as a sum of exponentials whose decay constants were known from the scattering angle and the diffusion coefficients, and whose amplitudes were related to the concentrations of reactants and products. Scattering experiments at 22 °C gave a bimolecular rate constant of 1.02 × 107m−1 s−1, while infectivity assays at 30 °C gave a rate constant of 1.28 × 107. Adjustment of both rate constants to 20 °C, assuming diffusion controlled reaction, gave 0.97 × 107 and 0.98 × 107m−1 s−1, respectively. This rate is about 1500 that predicted by Smoluchowski theory for a diffusion controlled reaction between two spherical particles; the discrepancy is largely explicable from orientational factors.  相似文献   

5.
Organic–inorganic halide perovskite single crystals possess many outstanding properties conducive for photovoltaic and optoelectronic applications. However, a clear photophysics picture is still elusive, particularly, their surface and bulk photophysics are inexorably convoluted by the spectral absorbance, defects, coexisting photoexcited species, etc. In this work, an all‐optical study is presented that clearly distinguishes the surface kinetics from those of the bulk in the representative methylammonium‐lead bromide (MAPbBr3) and ‐lead iodide (MAPbI3) single crystals. It is found that the bulk recombination lifetime of the MAPbBr3 single crystal is shortened significantly by approximately one to two orders (i.e., from ≈34 to ≈1 ns) at the surface with a surface recombination velocity of around 6.7 × 103 cm s?1. The surface trap density is estimated to be around 6.0 × 1017 cm?3, which is two orders larger than that of the bulk (5.8 × 1015 cm?3). Correspondingly, the diffusion length of the surface excited species is ≈130–160 nm, which is considerably reduced compared to the bulk value of ≈2.6–4.3 μm. Furthermore, the surface region has a wider bandgap that possibly arises from the strong lattice deformation. The findings provide new insights into the intrinsic photophysics essential for single crystal perovskite photovoltaics and optoelectronic devices.  相似文献   

6.
Owing to its high theoretical specific capacity (1166 mA h g?1) and particularly its advantage to be paired with a lithium‐metal‐free anode, lithium sulfide (Li2S) is regarded as a much safer cathode for next‐generation advanced lithium–sulfur (Li–S) batteries. However, the low conductivity of Li2S and particularly the severe “polysulfide shuttle” of lithium polysulfide (LiPS) dramatically hinder their practical application in Li–S batteries. To address such issues, herein a bifuctional 3D metal sulfide‐decorated carbon sponge (3DTSC), which is constructed by 1D carbon nanowires cross‐linked with 2D graphene nanosheets with high conductivity and polar 0D metal sulfide nanodots with efficient electrocatalytic activity and strong chemical adsorption capability for LiPSs, is presented. Benefiting from the well‐designed multiscale, multidimensional 3D porous nanoarchitecture with high conductivity, and efficient electrocatalytic and absorption ability, the 3DTSC significantly mitigates LiPS shuttle, improves the utilization of Li2S, and facilitates the transport of electrons and ions. As a result, even with a high Li2S loading of 8 mg cm?2, the freestanding 3DTSC‐Li2S cathode without a polymer binder and metallic current collector delivers outstanding electrochemical performance with a high areal capacity of 8.44 mA h cm?2.  相似文献   

7.
A bifunctional hybrid electrolyte composed of mesoporous silica nanosheets and liquid electrolyte is achieved for lithium–sulfur (Li–S) batteries. This hybrid electrolyte possesses abundant mesopores (2.8 nm), thin feature (20 µm), and high ionic conductivity (1.17 × 10?1 mS cm?1) as well as a low interfacial resistance with electrodes. Such unique features not only enable the efficient inhibition of the growth of lithium dendrites, but also significantly prevents polysulfide shuttling. Consequently, a Li–S battery with this hybrid electrolyte exhibits a relatively high reversible capacity and good capacity retention.  相似文献   

8.
Although metallic lithium is regarded as the “Holy Grail” for next‐generation rechargeable batteries due to its high theoretical capacity and low overpotential, the uncontrollable Li dendrite growth, especially under high current densities and deep plating/striping, has inhibited its practical application. Herein, a 3D‐printed, vertically aligned Li anode (3DP‐VALi) is shown to efficiently guide Li deposition via a “nucleation within microchannel walls” process, enabling a high‐performance, dendrite‐free Li anode. Moreover, the microchannels within the microwalls are beneficial for promoting fast Li+ diffusion, supplying large space for the accommodation of Li during the plating/stripping process. The high‐surface‐area 3D anode design enables high operating current densities and high areal capacities. As a result, the Li–Li symmetric cells using 3DP‐VALi demonstrate excellent electrochemical performances as high as 10 mA cm?2/10 mAh cm?2 for 1500 h and 5 mA cm?2/20 mAh cm?2 for 400 h, respectively. Additionally, the Li–S and Li–LiFePO4 cells using 3DP‐VALi anodes present excellent cycling stability up to 250 and 800 cycles at a rate of 1 C, respectively. It is believed that these new findings could open a new window for dendrite‐free metal anode design and pave the way toward energy storage devices with high energy/power density.  相似文献   

9.
Aims: To investigate the relationships between sulfate‐reducing bacteria (SRB), growth conditions, bentonite densities and copper sulfide generation under circumstances relevant to underground, high‐level radioactive waste repositories. Methods and Results: Experiments took place 450 m underground, connected under in situ pressure to groundwater containing SRB. The microbial reduction of sulfate to sulfide and subsequent corrosion of copper test plates buried in compacted bentonite were analysed using radioactive sulfur (35SO42?) as tracer. Mass distribution of copper sulfide on the plates indicated a diffusive process. The relationship between average diffusion coefficients (Ds) and tested density (ρ) was linear. Ds (m2 s?1) = ?0·004 × ρ (kg m?3) + 8·2, decreasing by 0·2 Ds units per 50 kg m?3 increase in density, from 1·2 × 10?11 m2 s?1 at 1750 kg m?3 to 0·2 × 10?11 m2 s?1 at 2000 kg m?3. Conclusions: It is possible that sulfide corrosion of waste canisters in future radioactive waste repositories depends mainly on sulfide concentration at the boundary between groundwater and the buffer, which in turn depends on SRB growth conditions (e.g., sulfate accessibility, carbon availability and electron donors) and geochemical parameters (e.g., presence of ferrous iron, which immobilizes sulfide). Maintaining high bentonite density is also important in mitigating canister corrosion. Significance and Impact of the Study: The sulfide diffusion coefficients can be used in safety calculations regarding waste canister corrosion. The work supports findings that microbial activity in compacted bentonite will be restricted. The study emphasizes the importance of growth conditions for sulfate reduction at the groundwater boundary of the bentonite buffer and linked sulfide production.  相似文献   

10.
Covalent organic framework (COF) can grow into self‐exfoliated nanosheets. Their graphene/graphite resembling microtexture and nanostructure suits electrochemical applications. Here, covalent organic nanosheets (CON) with nanopores lined with triazole and phloroglucinol units, neither of which binds lithium strongly, and its potential as an anode in Li‐ion battery are presented. Their fibrous texture enables facile amalgamation as a coin‐cell anode, which exhibits exceptionally high specific capacity of ≈720 mA h g?1 (@100 mA g?1). Its capacity is retained even after 1000 cycles. Increasing the current density from 100 mA g?1 to 1 A g?1 causes the specific capacity to drop only by 20%, which is the lowest among all high‐performing anodic COFs. The majority of the lithium insertion follows an ultrafast diffusion‐controlled intercalation (diffusion coefficient, DLi+ = 5.48 × 10?11 cm2 s?1). The absence of strong Li‐framework bonds in the density functional theory (DFT) optimized structure supports this reversible intercalation. The discrete monomer of the CON shows a specific capacity of only 140 mA h g?1 @50 mA g?1 and no sign of lithium intercalation reveals the crucial role played by the polymeric structure of the CON in this intercalation‐assisted conductivity. The potentials mapped using DFT suggest a substantial electronic driving‐force for the lithium intercalation. The findings underscore the potential of the designer CON as anode material for Li‐ion batteries.  相似文献   

11.
Z‐scheme‐inspired tandem photoelectrochemical (PEC) cells have received attention as a sustainable platform for solar‐driven CO2 reduction. Here, continuously 3D‐structured, electrically conductive titanium nitride nanoshells (3D TiN) for biocatalytic CO2‐to‐formate conversion in a bias‐free tandem PEC system are reported. The 3D TiN exhibits a periodically porous network with high porosity (92.1%) and conductivity (6.72 × 104 S m?1), which allows for high enzyme loading and direct electron transfer (DET) to the immobilized enzyme. It is found that the W‐containing formate dehydrogenase from Clostridium ljungdahlii (ClFDH) on the 3D TiN nanoshell is electrically activated through DET for CO2 reduction. At a low overpotential of 40 mV, the 3D TiN‐ClFDH stably converts CO2 to formate at a rate of 0.34 µmol h?1 cm?2 and a faradaic efficiency (FE) of 93.5%. Compared to a flat TiN‐ClFDH, the 3D TiN‐ClFDH shows a 58 times higher formate production rate (1.74 µmol h?1 cm?2) at 240 mV of overpotential. Lastly, a bias‐free biocatalytic tandem PEC cell that converted CO2 to formate at an average rate of 0.78 µmol h?1 and an FE of 77.3% only using solar energy and water is successfully assembled.  相似文献   

12.
Lithium–sulfur (Li–S) batteries have great promise to support the next‐generation energy storage if their sluggish redox kinetics and polysulfide shuttling can be addressed. The rational design of sulfur electrodes plays key roles in tacking these problems and achieving high‐efficiency sulfur electrochemistry. Herein, a synergetic defect and architecture engineering strategy to design highly disordered spinel Ni–Co oxide double‐shelled microspheres (NCO‐HS), which consist of defective spinel NiCo2O4–x (x = 0.9 if all nickel is Ni2+ and cobalt is Co2.13+), as the multifunctional sulfur host material is reported. The in situ constructed cation and anion defects endow the NCO‐HS with significantly enhanced electronic conductivity and superior polysulfide adsorbability. Meanwhile, the delicate nanoconstruction offers abundant active interfaces and reduced ion diffusion pathways for efficient Li–S chemistry. Attributed to these synergistic features, the sulfur composite electrode achieves excellent rate performance up to 5 C, remarkable cycling stability over 800 cycles and good areal capacity of 6.3 mAh cm?2 under high sulfur loading. This proposed strategy based on synergy engineering could also inform material engineering in related energy storage and conversion fields.  相似文献   

13.
Indolizine derivatives are of great interest as fluorescent emitters for peroxyoxalate chemiluminescence. The reaction of peroxyoxalates such as bis‐(2,4,6‐trichlorophenyl) oxalate (TCPO) with H2O2 can transfer energy to fluorescer via the formation of dioxetanedione intermediate. Four indolizine derivatives were used as a novel fluorescer in the chemiluminescence (CL) systems in this study. The relationship between CL intensity and the concentration of fluorescer, peroxyoxalate, sodium salicylate and hydrogen peroxide was investigated. Optimum conditions were obtained for four fluorescers and it was found that the indolizine can be used as an efficient green fluorescence emitter. Vitamin B6 induces a sharp decrease in the CL intensity of the TCPO–hydrogen peroxide–sodium salicylate system. A simple, rapid and sensitive CL method for the determination of vitamin B6 has been developed. The results showed a linear relationship between vitamin B6 concentration and peroxyoxalate CL intensity in the range 7.0 × 10−8–1.0 × 10−4. A detection limit of 2.3 × 10−8 M and relative standard deviation (RSD) of < 4.5% were obtained. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

14.
The relationship between leaf resistance to water vapour diffusion and each of the factors leaf water potential, light intensity and leaf temperature was determined for leaves on seedling apple trees (Malus sylvestris Mill. cv. Granny Smith) in the laboratory. Leaf cuticular resistance was also determined and transpiration was measured on attached leaves for a range of conditions. Leaf resistance was shown to be independent of water potential until potential fell below — 19 bars after which leaf resistance increased rapidly. Exposure of leaves to CO2-free air extended the range for which resistance was independent of water potential to — 30 bars. The light requirement for minimum leaf resistance was 10 to 20 W m?2 and at light intensities exceeding these, leaf resistance was unaffected by light intensity. Optimum leaf temperature for minimum diffusion resistance was 23 ± 2°C. The rate of change measured in leaf resistance in leaves given a sudden change in leaf temperature increased as the magnitude of the temperature change increased. For a sudden change of 1°C in leaf temperature, diffusion resistance changed at a rate of 0.01 s cm?1 min?1 whilst for a 9°C leaf temperature change, diffusion resistance changed at a rate of 0.1 s cm?1 min?1. Cuticular resistance of these leaves was 125 s cm?1 which is very high compared with resistances for open stomata of 1.5 to 4 s cm?1 and 30 to 35 s cm?1 for stomata closed in the dark. Transpiration was measured in attached apple leaves enclosed in a leaf chamber and exposed to a range of conditions of leaf temperature and ambient water vapour density. Peak transpiration of approximately 5 × 10?6 g cm?2 s?1 occurred at a vapour density gradient from the leaf to the air of 12 to 14 g m?3 after which transpiration declined due presumably to increased stomatal resistance. Leaves in CO2-free air attained a peak transpiration of 11 × 10?6 g cm?2 s?1 due to lower values of leaf resistance in CO2 free air. Transpiration then declined in these leaves due to development of an internal leaf resistance (of up to 2 s cm?1). The internal resistance was masked in leaves at normal CO2 concentrations by the increase in stomatal resistance.  相似文献   

15.
Li2S is one of the most promising cathode materials for Li‐ion batteries because of its high theoretical capacity and compatibility with Li‐metal‐free anode materials. However, the poor conductivity and electrochemical reactivity lead to low initial capacity and severe capacity decay. In this communication, a nitrogen and phosphorus codoped carbon (N,P–C) framework derived from phytic acid doped polyaniline hydrogel is designed to support Li2S nanoparticles as a binder‐free cathode for Li–S battery. The porous 3D architecture of N and P codoped carbon provides continuous electron pathways and hierarchically porous channels for Li ion transport. Phosphorus doping can also suppress the shuttle effect through strong interaction between sulfur and the carbon framework, resulting in high Coulombic efficiency. Meanwhile, P doping in the carbon framework plays an important role in improving the reaction kinetics, as it may help catalyze the redox reactions of sulfur species to reduce electrochemical polarization, and enhance the ionic conductivity of Li2S. As a result, the Li2S/N,P–C composite electrode delivers a stable capacity of 700 mA h g?1 with average Coulombic efficiency of 99.4% over 100 cycles at 0.1C and an areal capacity as high as 2 mA h cm?2 at 0.5C.  相似文献   

16.
Niobates with shear ReO3 crystal structures are remarkably promising anode materials for Li+ batteries due to their large capacities, inherent safety, and high cycling stability. However, they generally suffer from limited rate capabilities rooted in their insufficient electronic and Li+ conductivities. Here, micrometer‐sized copper niobate (Cu2Nb34O87) bulk as a new anode material having a high electronic conductivity of 2.1 × 10?5 S cm?1 and an impressive average Li+ diffusion coefficient of ≈3.5 × 10?13 cm2 s?1 is exploited, which synergistically leads to an excellent rate capability (184 mAh g?1 at 10 C) while remaining a large reversible capacity and superior cycling stability. Moreover, the fast Li+ transport pathways of grain boundary (micrometer scale) → lattice deformation area (nanometer scale) → (010) crystallographic plane (angstrom scale) are demonstrated in Cu2Nb34O87. Therefore, these results could pave the way for practical application of Cu2Nb34O87 in high‐performance Li+ batteries.  相似文献   

17.
The semiarid and arid zones cover a quarter of the global land area and support one‐fifth of the world's human population. A significant fraction of the global soil–atmosphere exchange for climatically active gases occurs in semiarid and arid zones yet little is known about these exchanges. A study was made of the soil–atmosphere exchange of CH4, CO, N2O and NOx in the semiarid Mallee system, in north‐western Victoria, Australia, at two sites: one pristine mallee and the other cleared for approximately 65 years for farming (currently wheat). The mean (± standard error) rates of CH4 exchange were uptakes of ?3.0 ± 0.5 ng(C) m?2 s?1 for the Mallee and ?6.0 ± 0.3 ng(C) m?2 s?1 for the Wheat. Converting mallee forest to wheat crop increases CH4 uptake significantly. CH4 emissions were observed in the Mallee in summer and were hypothesized to arise from termite activity. We find no evidence that in situ growing wheat plants emit CH4, contrary to a recent report. The average CO emissions of 10.1 ± 1.8 ng(C) m?2 s?1 in the Mallee and 12.6 ± 2.0 ng(C) m?2 s?1 in the Wheat. The average N2O emissions were 0.5 ± 0.1 ng(N) m?2 s?1 from the pristine Mallee and 1.4 ± 0.3 ng(N) m?2 s?1 from the Wheat. The experimental results show that the processes controlling these exchanges are different to those in temperate systems and are poorly understood.  相似文献   

18.
We have constructed an apparatus for the simultaneous measurement of electrophoretic mobility, μ, and diffusion coefficient, D, of macromolecules and cells. It combines band electrophoresis in a vertical, sucrose-gradient stabilized column, with quasielastic laser light-scattering determination of the diffusion coefficient of the species within the band. The entire electrophoresis cell is scanned through the laser beam of the quasielastic laser light-scattering apparatus by a vertical translation stage. Total intensity light-scattering measurement at each point in the cell gives the macromolecular concentration at that point. Solvent viscosity and electrical potential are measured at each point in the cell. Application of this apparatus to resealed red blood cell ghosts and to bovine hemoglobin indicates that measurements of field, viscosity, and migration distance are reliable, and that electroosmosis is insignificant. Application to T4D bacteriophage gives μ20,w = (?1.05 ± 0.05) × 10?4 cm2/V sec and D20,w = (3.35 ± 0.10) × 10?8 cm2/sec for fiberless particles, and μ20,w = ?(0.59 ± 0.03) × 10?4 cm2/V sec and D20,w = (2.86 ± 0.09) × 10?8 cm2/sec for whole phage with 6 fibers. Approximate analysis of these results with the Henry electrophoresis theory for spheres in dicates that each fiber contributes about 193 positive charges to the phage particle, compared with 327 from amino-acid analysis. The advantages and disadvantages of this apparatus, relative to conventional electrophoresis and to electrophoretic light scattering, are discussed.  相似文献   

19.
Selenium–sulfur solid solutions are a class of potential cathode materials for high energy batteries, since they have higher theoretical capacities than selenium and improved conductivity over sulfur. Here, a high‐performance cathode material by confining 70 wt% of SeS2 in a highly ordered mesoporous carbon (CMK‐3) framework with a polydopamine (PDA) protection sheath for novel Li–Se/S batteries is reported. With a relatively high SeS2 mass loading of 2.6–3 mg cm?2, the CMK‐3/SeS2@PDA cathode exhibits a high capacity of >1200 mA h g?1 at 0.2 A g?1, excellent C‐rate capability of 535 mA h g?1 at 5 A g?1, and prolonged life over 500 cycles. Benefitting from the unique advantages of SeS2 and the rationally designed host framework, this new cathode material demonstrates a feasible strategy to overcome the bottlenecks of current Li–S systems for high energy density rechargeable batteries.  相似文献   

20.
Ar + H2 plasma interacting with liquid lithium was carried out on a one-cathode linear plasma device (SCU-PSI). The lithium sample was covered with capillary porous structure (CPS). It is found that the electron temperature of applied plasma ranged from ~0–1 eV and electron density ranged from 0.1 × 1020 to 1 × 1020 m?3. The experimental results indicate that a reduction in the electron temperature and the lithium evaporation is found as the percentage of H2 increases When the ratio of argon and hydrogen keeps constant, the electron temperature and lithium evaporation increase with applied input power, respectively. The retention of hydrogen atoms in lithium surface results in reducing the lithium evaporation. The XRD analysis result shows that during plasma radiation no LiH is formed.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号