China, People’s Republic
Significantly Enhanced Electrocatalytic Activity of Copper for Hydrogen Evolution Reaction Through Femtosecond Laser Blackening
Jan 2021
Publication
In this work we report on the creation of a black copper via femtosecond laser processing and its application as a novel electrode material. We show that the black copper exhibits an excellent electrocatalytic activity for hydrogen evolution reaction (HER) in alkaline solution. The laser processing results in a unique microstructure: microparticles covered by finer nanoparticles on top. Electrochemical measurements demonstrate that the kinetics of the HER is significantly accelerated after bare copper is treated and turned black. At −0.325 V (v.s. RHE) in 1 M KOH aqueous solution the calculated area-specific charge transfer resistance of the electrode decreases sharply from 159 Ω cm2 for the untreated copper to 1 Ω cm2 for the black copper. The electrochemical surface area of the black copper is measured to be only 2.4 times that of the untreated copper and therefore the significantly enhanced electrocatalytic activity of the black copper for HER is mostly a result of its unique microstructure that favors the formation and enrichment of protons on the surface of copper. This work provides a new strategy for developing high-efficient electrodes for hydrogen generation.
Catalytic Effect of MoS2 on Hydrogen Storage Thermodynamics and Kinetics of an As-milled YMg11Ni Alloy
Jul 2017
Publication
In this study YMg11Ni and YMg11Ni + 5 wt% MoS2 (named YMg11Ni–MoS2) alloys were prepared by mechanical milling to examine the effect of adding MoS2 on the hydrogen storage performance of a Y–Mg–Ni-based alloy. The as-cast and milled alloys were tested to identify their structures by X-ray diffraction and transmission electron microscopy. The isothermal hydrogen storage thermodynamics and dynamics were identified through an automatic Sieverts apparatus and the non-isothermal dehydrogenation performance was investigated by thermogravimetry and differential scanning calorimetry. The dehydrogenation activation energy was calculated by both Arrhenius and Kissinger methods. Results revealed that adding MoS2produces a very slight effect on hydrogen storage thermodynamics but causes an obvious reduction in the hydrogen sorption and desorption capacities because of the deadweight of MoS2. The addition of MoS2significantly enhances the dehydrogenation performance of the alloy such as lowering dehydrogenation temperature and enhancing dehydrogenation rate. Specifically the initial desorption temperature of the alloy hydride lowers from 549.8 K to 525.8 K. The time required to desorb hydrogen at 3 wt% H2 is 1106 456 363 and 180 s corresponding to hydrogen desorption temperatures at 593 613 633 and 653 K for the YMg11Ni alloy and 507 208 125 and 86 s at identical conditions for the YMg11Ni–5MoS2 alloy. The dehydrogenation activation energy (Ea) values with and without added MoS2are 85.32 and 98.01 kJ mol−1. Thus a decrease in Ea value by 12.69 kJ mol−1 occurs and is responsible for the amelioration of the hydrogen desorption dynamics by adding a MoS2 catalyst.
The Hydrogen Storage Properties of MgH2–Fe7S8 Composites
Nov 2020
Publication
Nanostructured Fe7S8 was successfully synthesized and its catalytic effect on hydrogen absorption/desorption performance of MgH22 is systemically discussed. The MgH2 + 16.7 wt% Fe7S8 composite prepared by ball-milling method offers a striking catalytic activity for hydrogenation kinetics and also reduces the initial decomposition temperature for MgH22. The composite of MgH2–Fe7S8 can absorb 4.000 wt% of hydrogen within 1800 s at 473 K which is about twice that of pristine MgH2 (1.847 wt%) under the same conditions. The onset hydrogen release temperature of Fe7S8-modified MgH2 is 420 K which is 290 K lower than that of additive-free MgH2 (710 K). Meanwhile the doped sample could release 4.403 wt% of hydrogen within 1800 s at 623 K as compared to 2.479 wt% of hydrogen by MgH2. The activation energy for MgH2–Fe7S8 is about 130.0 kJ mol−1 approximately 36 kJ mol−1 lower than that of MgH2. The hydriding process of MgH2 + 16.7 wt% Fe7S8 follows the nucleation and growth mechanism. The prominent hydrogen storage performances are related to the reactions between MgH2 and Fe7S8. The newly formed MgS and Fe in the ball-milling process present a co-catalytic effect on the hydrogen storage performance of MgH22.
The Impact of Disruptive Powertrain Technologies on Energy Consumption and Carbon Dioxide Emissions from Heavy-duty Vehicles
Jan 2020
Publication
Minimising tailpipe emissions and the decarbonisation of transport in a cost effective way remains a major objective for policymakers and vehicle manufacturers. Current trends are rapidly evolving but appear to be moving towards solutions in which vehicles which are increasingly electrified. As a result we will see a greater linkage between the wider energy system and the transportation sector resulting in a more complex and mutual dependency. At the same time major investments into technological innovation across both sectors are yielding rapid advancements into on-board energy storage and more compact/lightweight on-board electricity generators. In the absence of sufficient technical data on such technology holistic evaluations of the future transportation sector and its energy sources have not considered the impact of a new generation of innovation in propulsion technologies. In this paper the potential impact of a number of novel powertrain technologies are evaluated and presented. The analysis considers heavy duty vehicles with conventional reciprocating engines powered by diesel and hydrogen hybrid and battery electric vehicles and vehicles powered by hydrogen fuel cells and freepiston engine generators (FPEGs). The benefits are compared for each technology to meet the expectations of representative medium and heavy-duty vehicle drivers. Analysis is presented in terms of vehicle type vehicle duty cycle fuel economy greenhouse gas (GHG) emissions impact on the vehicle etc.. The work shows that the underpinning energy vector and its primary energy source are the most significant factor for reducing primary energy consumption and net CO2 emissions. Indeed while an HGV with a BEV powertrain offers no direct tailpipe emissions it produces significantly worse lifecycle CO2 emissions than a conventional diesel powertrain. Even with a de-carbonised electricity system (100 g CO2/kWh) CO2 emissions are similar to a conventional Diesel fuelled HGV. For the HGV sector range is key to operator acceptability of new powertrain technologies. This analysis has shown that cumulative benefits of improved electrical powertrains on-board storage efficiency improvements and vehicle design in 2025 and 2035 mean that hydrogen and electric fuelled vehicles can be competitive on gravimetric and volumetric density. Overall the work demonstrates that presently there is no common powertrain solution appropriate for all vehicle types but how subtle improvements at a vehicle component level can have significant impact on the design choices for the wider energy system.
Hydrogen Diffusion Mechanism around a Crack Tip in Type 304L Austenite Stainless Steel Considering the Influence of the Volume Expansion of Strain-Induced Martensite Transformation
Sep 2019
Publication
Strain-induced martensite transformation (SIMT) commonly exists around a crack tip of metastable austenite stainless steels. The influence of the volume expansion of the SIMT on the hydrogen diffusion was investigated by hydrogen diffusion modelling around a crack tip in type 304L austenite stainless steel. The volume expansion changed the tensile stress state into pressure stress state at the crack tip resulting in a large stress gradient along the crack propagation direction. Compared to the analysis without considering the volume expansion effect this volume expansion further accelerated the hydrogen transport from the inner surface to a critical region ahead of the crack tip and further increased the maximum value of the hydrogen concentration at the critical position where the strain-induced martensite fraction approximates to 0.1 indicating that the volume expansion of the SIMT further increased the hydrogen embrittlement susceptibility.
Experimental Investigation of the Effect of Hydrogen on Fracture Toughness of 2.25Cr-1Mo-0.25V Steel and Welds after Annealing
Mar 2018
Publication
Hydrogen embrittlement (HE) is a critical issue that hinders the reliability of hydrogenation reactors. Hence it is of great significance to investigate the effect of hydrogen on fracture toughness of 2.25Cr-1Mo-0.25V steel and weld. In this work the fracture behavior of 2.25Cr-1Mo-0.25V steel and welds was studied by three-point bending tests under hydrogen-free and hydrogen-charged conditions. The immersion charging method was employed to pre-charge hydrogen inside specimen and the fracture toughness of these joints was evaluated quantitatively. The microstructure and grain size of the specimens were observed by scanning electron microscopy (SEM) and by metallurgical microscopy to investigate the HE mechanisms. It was found that fracture toughness for both the base metal (BM) and the weld zone (WZ) significantly decreased under hydrogen-charged conditions due to the coexistence of the hydrogen-enhanced decohesion (HEDE) and hydrogen-enhanced localized plasticity (HELP) mechanisms. Moreover the formation and growth of primary voids were observed in the BM leading to a superior fracture toughness. In addition the BM compared to the WZ shows superior resistance to HE because the finer grain size in the BM leads to a larger grain boundary area thus distributing more of the diffusive hydrogen trapped in the grain boundary and reducing the hydrogen content.
Location-dependent Effect of Nickel on Hydrogen Dissociation and Diffusion on Mg (0001) Surface: Insights into Hydrogen Storage Material Design
Apr 2021
Publication
Density functional theory (DFT) calculations have been performed to investigate the hydrogen dissociation and diffusion on Mg (0001) surface with Ni incorporating at various locations. The results show that Ni atom is preferentially located inside Mg matrix rather than in/over the topmost surface. Further calculations reveal that Ni atom locating in/over the topmost Mg (0001) surface exhibits excellent catalytic effect on hydrogen dissociation with an energy barrier of less than 0.05 eV. In these cases the rate-limiting step has been converted from hydrogen dissociation to surface diffusion. In contrast Ni doping inside Mg bulk not only does little help to hydrogen dissociation but also exhibits detrimental effect on hydrogen diffusion. Therefore it is crucial to stabilize the Ni atom on the surface or in the topmost layer of Mg (0001) surface to maintain its catalytic effect. For all the case of Ni-incorporated Mg (0001) surfaces the hydrogen atom prefers firstly immigrate along the surface and then penetrate into the bulk. It is expected that the theoretical findings in the present study could offer fundamental guidance to future designing on efficient Mg-based hydrogen storage materials.
Production of High-purity Hydrogen from Paper Recycling Black Liquor via Sorption Enhanced Steam Reforming
Jul 2020
Publication
Environmentally friendly and energy saving treatment of black liquor (BL) a massively produced waste in Kraft papermaking process still remains a big challenge. Here by adopting a Ni-CaO-Ca12Al14O33 bifunctional catalyst derived from hydrotalcite-like materials we demonstrate the feasibility of producing high-purity H2 (∼96%) with 0.9 mol H2 mol-1 C yield via the sorption enhanced steam reforming (SESR) of BL. The SESRBL performance in terms of H2 production maintained stable for 5 cycles but declined from the 6th cycle. XRD Raman spectroscopy elemental analysis and energy dispersive techniques were employed to rationalize the deactivation of the catalyst. It was revealed that gradual sintering and agglomeration of Ni and CaO and associated coking played important roles in catalyst deactivation and performance degradation of SESRBL while deposition of Na and K from the BL might also be responsible for the declined performance. On the other hand it was demonstrated that the SESRBL process could effectively reduce the emission of sulfur species by storing it as CaSO3. Our results highlight a promising alternative for BL treatment and H2 production thereby being beneficial for pollution control and environment governance in the context of mitigation of climate change.
Analysis of Hydrogen Production Potential from Waste Plastics by Pyrolysis and In Line Oxidative Steam Reforming
Oct 2021
Publication
A study was carried out on the valorization of different waste plastics (HDPE PP PS and PE) their mixtures and biomass/HDPE mixtures by means of pyrolysis and in line oxidative steam reforming. A thermodynamic equilibrium simulation was used for determining steam reforming data whereas previous experimental results were considered for setting the pyrolysis volatile stream composition. The adequacy of this simulation tool was validated using experimental results obtained in the pyrolysis and in line steam reforming of different plastics. The effect the most relevant process conditions i.e. temperature steam/plastic ratio and equivalence ratio have on H2 production and reaction enthalpy was evaluated. Moreover the most suitable conditions for the oxidative steam reforming of plastics of different nature and their mixtures were determined. The results obtained are evidence of the potential interest of this novel valorization route as H2 productions of up to 25 wt% were obtained operating under autothermal conditions.
An Optimal Fuzzy Logic-Based Energy Management Strategy for a Fuel Cell/Battery Hybrid Power Unmanned Aerial Vehicle
Feb 2022
Publication
With the development of high-altitude and long-endurance unmanned aerial vehicles (UAVs) optimization of the coordinated energy dispatch of UAVs’ energy management systems has become a key target in the research of electric UAVs. Several different energy management strategies are proposed herein for improving the overall efficiency and fuel economy of fuel cell/battery hybrid electric power systems (HEPS) of UAVs. A rule-based (RB) energy management strategy is designed as a baseline for comparison with other strategies. An energy management strategy (EMS) based on fuzzy logic (FL) for HEPS is presented. Compared with classical rule-based strategies the fuzzy logic control has better robustness to power fluctuations in the UAV. However the proposed FL strategy has an inherent defect: the optimization performances will be determined by the heuristic method and the past experiences of designers to a great extent rather than a specific cost function of the algorithm itself. Thus the paper puts forward an improved fuzzy logic-based strategy that uses particle swarm optimization (PSO) to track the optimal thresholds of membership functions and the equivalent hydrogen consumption minimization is considered as the objective function. Using a typical 30 min UAV mission profile all the proposed EMS were verified by simulations and rapid controller prototype (RCP) experiments. Comprehensive comparisons and analysis are presented by evaluating hydrogen consumption system efficiency and voltage bus stability. The results show that the PSO-FL algorithm can further improve fuel economy and achieve superior overall dynamic performance when controlling a UAV’s fuel-cell powertrain.
Molecular Dynamics Studies of Hydrogen Effect on Intergranular Fracture in α-Iron
Nov 2020
Publication
In the current study the effect of hydrogen atoms on the intergranular failure of α-iron is examined by a molecular dynamics (MD) simulation. The effect of hydrogen embrittlement on the grain boundary (GB) is investigated by diffusing hydrogen atoms into the grain boundaries using a bicrystal body-centered cubic (BCC) model and then deforming the model with a uniaxial tension. The Debye Waller factors are applied to illustrate the volume change of GBs and the simulation results suggest that the trapped hydrogen atoms in GBs can therefore increase the excess volume of GBs thus enhancing intergranular failure. When a constant displacement loading is applied to the bicrystal model the increased strain energy can barely be released via dislocation emission when H is present. The hydrogen pinning effect occurs in the current dislocation slip system <111>{112}. The hydrogen atoms facilitate cracking via a decrease of the free surface energy and enhance the phase transition via an increase in the local pressure. Hence the failure mechanism is prone to intergranular failure so as to release excessive pressure and energy near GBs. This study provides a mechanistic framework of intergranular failure and a theoretical model is then developed to predict the intergranular cracking rate
Vented Hydrogen-air Explosion in a Small Obstructed Rectangular Container- effect of the Blockage Ratio
Sep 2019
Publication
The explosion venting is an effective way to reduce hydrogen-air explosion hazards but the explosion venting has been hardly touched in an obstructed container. Current experiments focused on the effects of different blockage ratios on the explosion venting in a small obstructed rectangular container. Experimental results show that three overpressure peaks are formed in the case with the obstacle while only two can be observed in the case of no obstacle. The obstacle blockage ratio has a significant influence on the peak overpressure induced by the obstacle-acoustic interactions but it has an ignorable effect on the peak overpressure caused by the rupture of the vent film. The obstacle-induced overpressure peak first increases and then decreases with the increase of the blockage ratio. In addition all overpressure peaks inside the container decreases with the increase of the vent area and its appearance time is relatively earlier for larger vent area.
Simulation Analysis on the Risk of Hydrogen Releases and Combustion in Subsea Tunnels
Oct 2015
Publication
Hydrogen is considered to be a very promising potential energy carrier due to its excellent characteristics such as abundant resources high fuel value clean and renewable. Its safety features greatly influence the potential use. Several safety problems need to be analyzed before using in transportation industry. With the development of the tunnel transportation technology the safe use of hydrogen in tunnels will receive a lot of research attentions. In this article the risk associated with hydrogen release from onboard high-pressure vessels and the induced combustion in tunnels was analyzed using the Partially Averaged Navier–Stokes (PANS) turbulence model. The influences of the tunnel ventilation facilities on the hydrogen flow characteristics and the flammable hydrogen cloud sizes were studied. The tunnel layouts were designed according to the subsea tunnel. And a range of longitudinal ventilation conditions had been considered to investigate the hydrogen releases and the sizes of the flammable hydrogen cloud. Then the hydrogen combustion simulation was carried out after the fixed leaking time. The overpressures induced after the ignition of leaking hydrogen were studied. The influences of ventilation and ignition delay time on the overpressure were also investigated. The main aim was to research the phenomena of hydrogen releases and combustion risk inside subsea tunnels and to lay the foundation of risk assessment methodology developed for hydrogen energy applications on transportation.
Blending Ammonia into Hydrogen to Enhance Safety through Reduced Burning Velocity
Sep 2019
Publication
Laminar burning velocities (SL) of hydrogen/ammonia mixtures in air at atmospheric pressure were studied experimentally and numerically. The blending of hydrogen with ammonia two fuels that have been proposed as promising carriers for renewable energy causes the laminar flame speed of the mixture SL to decrease significantly. However details of this have not previously available. Systematic measurements were therefore performed for a series of hydrogen/ammonia mixtures with wide ranges of mole fractions of blended ammonia (XNH3) and equivalence ratio using a heat flux method based on heat flux of a flat flame transferred to the burner surface. It was found that the mixture of XNH3 = 40% has a value of SL close to that of methane which is the dominant component of natural gas. Using three chemical kinetic mechanisms available in the literature i.e. the well-known GRI-Mech 3.0 mechanism and two mechanisms recently released SL were also modelled for the cases studied. However the discrepancies between the experimental and numerical results can exceed 50% with the GRI-Mech 3.0 mechanism. Discrepancies were also found between the numerical results obtained with different mechanisms. These results can contribute to an increase in both the safety and efficiency of the coutilization of these two types of emerging renewable fuel and to guiding the development of better kinetic models.
Application of DFT Simulation to the Investigation of Hydrogen Embrittlement Mechanism and Design of High Strength Low Alloy Steel
Dec 2022
Publication
In this work first-principles methods were performed to simulate interactions between hydrogen and common alloying elements of high strength low alloy (HSLA) steel. The world has been convinced that hydrogen could be one of the future clean energy sources. HSLA steel with a balance of strength toughness and hydrogen embrittlement susceptibility is expected for application in large-scale hydrogen storage and transportation. To evaluate the property deterioration under a hydrogen atmosphere hydrogen embrittlement (HE) of HSLA steel attracts attention. However due to the small size of hydrogen atoms the mechanism of HE is challenging to observe directly by current experimental methods. To understand the HE mechanism at an atomic level DFT methods were applied to simulate the effects of alloying elements doping in bcc-Fe bulk structure and grain boundary structure. Furthermore the potential application of DFT to provide theoretical advice for HSLA steel design is discussed.
To Adopt CCU Technology or Not? An Evolutionary Game between Local Governments and Coal-Fired Power Plants
Apr 2022
Publication
Carbon dioxide capture and utilization (CCU) technology is a significant means by which China can achieve its ambitious carbon neutrality goal. It is necessary to explore the behavioral strategies of relevant companies in adopting CCU technology. In this paper an evolutionary game model is established in order to analyze the interaction process and evolution direction of local governments and coal-fired power plants. We develop a replicator dynamic system and analyze the stability of the system under different conditions. Based on numerical simulation we analyze the impact of key parameters on the strategies of stakeholders. The simulation results show that the unit prices of hydrogen and carbon dioxide derivatives have the most significant impact: when the unit price of hydrogen decreases to 15.9 RMB/kg or the unit price of carbon dioxide derivatives increases to 3.4 RMB/kg the evolutionary stabilization strategy of the system changes and power plants shift to adopt CCU technology. The results of this paper suggest that local governments should provide relevant support policies and incentives for CCU technology deployment as well as focusing on the synergistic development of CCU technology and renewable energy hydrogen production technology
Heat Transfer Analysis for Fast Filling of On-board Hydrogen Tank
Mar 2019
Publication
The heat transfer analysis in the filling process of compressed on-board hydrogen storage tank has been the focus of hydrogen storage research. The initial conditions mass flow rate and heat transfer coefficient have certain influence on the hydrogen filling performance. In this paper the effects of mass flow rate and heat transfer coefficient on hydrogen filling performance are mainly studied. A thermodynamic model of the compressed hydrogen storage tank was established by Matlab/Simulink. This 0D model is utilized to predict the hydrogen temperature hydrogen pressure tank wall temperature and SOC (State of Charge) during filling process. Comparing the simulated results with the experimental data the practicability of the model can be verified. The simulated results have certain meaning for improving the hydrogenation parameters in real filling process. And the model has a great significance to the study of hydrogen filling and purification.
Predicting Radiative Characteristics of Hydrogen and Hythane Jet Fires Using Firefoam
Sep 2013
Publication
A possible consequence of pressurized hydrogen release is an under-expanded jet fire. Knowledge of the flame length radiative heat flux and fraction as well as the effects of variations in ground reflectance is important for safety assessment. The present study applies an open source CFD code FireFOAM to study the radiation characteristics of hydrogen and hydrogen/methane jet fires. For combustion the eddy dissipation concept for multi-component fuels recently developed by the authors in the large eddy simulation (LES) framework is used. The radiative heat is computed with the finite volume discrete ordinates model in conjunction with the weighted-sum-of-gray-gases model for the absorption/emission coefficient. The pseudo-diameter approach is used in which the corresponding parameters are calculated using the correlations of Birch et al. [22]. The predicted flame length and radiant fraction are in good agreement with the measurements of Schefer et al. [2] Studer et al. [3] and Ekoto et al. [6]. In order to account for the effects of variation in ground surface reflectance the emissivity of hydrogen flames was modified following Ekoto et al. [6]. Four cases with different ground reflectance are computed. The predictions show that the ground surface reflectance only has minor effect on the surface emissive power of the hydrogen jet fire. The radiant fractions fluctuate from 0.168 to 0.176 close to the suggested value of 0.16 by Ekoto et al.[6] based on the analysis of their measurements.
RBD-fast Based Sensitivity and Uncertainty Analysis on a Computational Hydrogen Recombiner Test Case
Sep 2017
Publication
Deflagration-to-Detonation Transition Ratio (DDTR) is an important parameter in measuring the hazard of hydrogen detonation at given thermodynamic conditions. It’s among the major tasks to evaluate DDTR in the study of hydrogen safety in a nuclear containment. With CFD tools detailed distribution of thermodynamic parameters at each instant can be simulated with considerable reliability. Then DDTR can be estimated using related CFD output. Forstochastic or epistemic reasons uncertainty always exists in input parameters during computations. This lack of accuracy can finally be reflected in the uncertainty of computation results e.g. DDTR in our consideration. The analysis of the influence of the input uncertainty is therefore a key step to understand the model’s response on the output and possibly to improve the accuracy. The increase of computational power makes it possible to perform statistics-based sensitivity and uncertainty (SU) analysis on CFD simulations. This paper aims at presenting some ideas on the procedure in safety analysis on hydrogen in nuclear containment. A hydrogen recombiner case is constructed and simulated with CFD method. DDTR at each instant is computed using a semi-empirical method. RBD-FAST based SU analysis is performed on the result.
A Study on the Influential Factors of Stress Corrosion Cracking in C110 Casing Pipe
Jan 2022
Publication
In this paper we analyze the potential factors affecting the hydrogen sulfide type of stress corrosion cracking in C110 casing pipes. In order to further study these cracking factors the methods of material property testing scanning electron microscopy XRD TEM and 3D ultra-depth-of-field were applied in the experiments. Besides that an HTHP autoclave was independently designed by the laboratory to simulate the actual corrosion environment and the potential factors affecting the stress corrosion cracking of C110 casing pipes were determined. The test results showed that the chemical composition metallographic structure hardness and non-metallic inclusions of the two types of C110 casing pipes were all qualified. In fact there remains a risk of stress corrosion cracking when the two kinds of C110 casing pipes serve under long-term field-working conditions. It is considered in this paper that the precipitates on the material surface stress damage and pitting corrosion are all critical factors affecting the stress corrosion cracking of casing pipes.
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