United States
Recent Advances in Carbon Dioxide Conversion: A Circular Bioeconomy Perspective
Jun 2021
Publication
Managing the concentration of atmospheric CO2 requires a multifaceted engineering strategy which remains a highly challenging task. Reducing atmospheric CO2 (CO2R) by converting it to value-added chemicals in a carbon neutral footprint manner must be the ultimate goal. The latest progress in CO2R through either abiotic (artificial catalysts) or biotic (natural enzymes) processes is reviewed herein. Abiotic CO2R can be conducted in the aqueous phase that usually leads to the formation of a mixture of CO formic acid and hydrogen. By contrast a wide spectrum of hydrocarbon species is often observed by abiotic CO2R in the gaseous phase. On the other hand biotic CO2R is often conducted in the aqueous phase and a wide spectrum of value-added chemicals are obtained. Key to the success of the abiotic process is understanding the surface chemistry of catalysts which significantly governs the reactivity and selectivity of CO2R. However in biotic CO2R operation conditions and reactor design are crucial to reaching a neutral carbon footprint. Future research needs to look toward neutral or even negative carbon footprint CO2R processes. Having a deep insight into the scientific and technological aspect of both abiotic and biotic CO2R would advance in designing efficient catalysts and microalgae farming systems. Integrating the abiotic and biotic CO2R such as microbial fuel cells further diversifies the spectrum of CO2R.
Controlled Hydrogen Fleet and Infrastructure Demonstration and Validation Project
Dec 2011
Publication
This report summarizes the work conducted under U.S. Department of Energy (DOE) under contract DE-FC36-04GO14285 by Mercedes-Benz & Research Development North America (MBRDNA) Chrysler Daimler Mercedes Benz USA (MBUSA) BP DTE Energy and NextEnergy to validate fuel cell technologies for infrastructure transportation as well as assess technology and commercial readiness for the market. The Mercedes Team together with its partners tested the technology by operating and fuelling hydrogen fuel cell vehicles under real world conditions in varying climate terrain and driving conditions. Vehicle and infrastructure data was collected to monitor the progress toward the hydrogen vehicle and infrastructure performance targets of $2.00 to 3.00/gge hydrogen production cost and 2000-hour fuel cell durability. Finally to prepare the public for a hydrogen economy outreach activities were designed to promote awareness and acceptance of hydrogen technology. DTE BP and NextEnergy established hydrogen filling stations using multiple technologies for on-site hydrogen generation storage and dispensing. DTE established a hydrogen station in Southfield Michigan while NextEnergy and BP worked together to construct one hydrogen station in Detroit. BP constructed another fueling station in Burbank California and provided a full-time hydrogen trailer at San Francisco California and a hydrogen station located at Los Angeles International Airportmore.
Evaluation of Decarbonization Technologies for ASEAN Countries via an Integrated Assessment Tool
May 2022
Publication
A new assessment tool for evaluating decarbonization technologies that considers each technology’s sustainability security affordability readiness and impact for a specific country is proposed. This tool is applied to a set of decarbonization technologies for the power transport and industry sectors for the ten Southeast Asian countries that constitute ASEAN. This results in a list of the most promising decarbonization technologies as well as the remaining issues that need more research and development. This study reveals several common themes for ASEAN’s decarbonization. First carbon capture and storage (CCS) is a key technology for large-scale CO2 emission. Second for countries that rely heavily on coal for power generation switching to gas can halve their CO2 emission in the power sector and should be given high priority. Third hydropower and bioenergy both have high potential for the majority of ASEAN countries if their sustainability issues can be resolved satisfactorily. Fourth replacing conventional vehicles by electric vehicles is the overarching theme in the road transport sector but will result in increased demand for electricity. In the medium to long term the use of hydrogen for marine fuel and biofuels for aviation fuel are preferred solutions for the marine and aviation transport sectors. Fifth for the industry sector installing CCS in industrial plants should be given priority but replacing fossil fuels by blue hydrogen for high-temperature heating is the preferred long-term solution.
Metastable Metal Hydrides for Hydrogen Storage
Oct 2012
Publication
The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. On the other hand the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.
Physicochemical Properties of Proton-conducting SmNiO3 Epitaxial Films
Mar 2019
Publication
Proton conducting SmNiO3 (SNO) thin films were grown on (001) LaAlO3 substrates for systematically investigating the proton transport properties. X-ray Diffraction and Atomic Force Microscopy studies reveal that the as-grown SNO thin films have good single crystallinity and smooth surface morphology. The electrical conductivity measurements in air indicate a peak at 473 K in the temperature dependence of the resistance of the SNO films probably due to oxygen loss on heating. A Metal-Insulator-Transition occurs at 373 K for the films after annealing at 873 K in air. In a hydrogen atmosphere (3% H2/97% N2) an anomalous peak in the resistance is found at 685 K on the first heating cycle. Electrochemical Impedance Spectroscopy studies as a function of temperature indicate that the SNO films have a high ionic conductivity (0.030 S/cm at 773 K) in a hydrogen atmosphere. The activation energy for proton conductivity was determined to be 0.23 eV at 473–773 K and 0.37 eV at 773–973 K respectively. These findings demonstrate that SNO thin films have good proton conductivity and are good candidate electrolytes for low temperature proton-conducting Solid Oxide Fuel Cells.
Comparison of Conventional vs. Modular Hydrogen Refuelling Stations and On-Site Production vs. Delivery
Mar 2017
Publication
To meet the needs of public and private stakeholders involved in the development construction and operation of hydrogen fuelling stations needed to support the widespread roll-out of hydrogen fuel cell electric vehicles this work presents publicly available station templates and analyses. These ‘Reference Stations’ help reduce the cost and speed the deployment of hydrogen stations by providing a common baseline with which to start a design enable quick assessment of potential sites for a hydrogen station identify contributors to poor economics and suggest areas of research. This work presents layouts bills of materials piping and instrumentation diagrams and detailed analyses of five new station designs. In the near term delivered hydrogen results in a lower cost of hydrogen compared to on-site production via steam methane reforming or electrolysis although the on-site production methods have other advantages. Modular station concepts including on-site production can reduce lot sizes from conventional assemble-on-site stations.
Water Photo-Oxidation Reaction on Clean and Doped Two-Dimensional Graphitic C2N
Apr 2020
Publication
In the search for new efficient photo-catalysts for hydrogen production through water splitting the main attention has been paid to tuning the band gap width and its position with respect to vacuum level. However actual electro-catalytic activity for the water oxidation reaction on a catalyst surface is no less important than those quantities. In this work we evaluate from first principles the thermodynamics of the reaction on relatively new candidates for water splitting: two-dimensional C2N and that doped with phosphorus. We find that the 4-step reaction usually expected for water splitting will not proceed on these systems resulting in oxygen atoms left strongly adsorbed to the surface. Another option a 3-step reaction is also found to be unfavorable. We also test an effect of higher oxygen coverage on the reaction thermodynamics as suggested elsewhere. We find that indeed the doubled O-coverage makes the 4-step reaction feasible for the doped C2N. However an unacceptably high anode potential is required to make this reaction proceed. We thus conclude that the materials under consideration may not be efficient electro-catalysts for water splitting.
Materials for Hydrogen-based Energy Storage - Past, Recent Progress and Future Outlook
Dec 2019
Publication
Michael Hirscher,
Volodymyr A. Yartys,
Marcello Baricco,
José Bellosta von Colbe,
Didier Blanchard,
Robert C. Bowman Jr.,
Darren P. Broom,
Craig Buckley,
Fei Chang,
Ping Chen,
Young Whan Cho,
Jean-Claude Crivello,
Fermin Cuevas,
William I. F. David,
Petra E. de Jongh,
Roman V. Denys,
Martin Dornheim,
Michael Felderhoff,
Yaroslav Filinchuk,
George E. Froudakis,
David M. Grant,
Evan MacA. Gray,
Bjørn Christian Hauback,
Teng He,
Terry D. Humphries,
Torben R. Jensen,
Sangryun Kim,
Yoshitsugu Kojima,
Michel Latroche,
Hai-wen Li,
Mykhaylo V. Lototskyy,
Joshua W. Makepeace,
Kasper T. Møller,
Lubna Naheed,
Peter Ngene,
Dag Noreus,
Magnus Moe Nygård,
Shin-ichi Orimo,
Mark Paskevicius,
Luca Pasquini,
Dorthe B. Ravnsbæk,
M. Veronica Sofianos,
Terrence J. Udovic,
Tejs Vegge,
Gavin Walker,
Colin Webb,
Claudia Weidenthaler and
Claudia Zlotea
Globally the accelerating use of renewable energy sources enabled by increased efficiencies and reduced costs and driven by the need to mitigate the effects of climate change has significantly increased research in the areas of renewable energy production storage distribution and end-use. Central to this discussion is the use of hydrogen as a clean efficient energy vector for energy storage. This review by experts of Task 32 “Hydrogen-based Energy Storage” of the International Energy Agency Hydrogen TCP reports on the development over the last 6 years of hydrogen storage materials methods and techniques including electrochemical and thermal storage systems. An overview is given on the background to the various methods the current state of development and the future prospects. The following areas are covered; porous materials liquid hydrogen carriers complex hydrides intermetallic hydrides electro-chemical storage of energy thermal energy storage hydrogen energy systems and an outlook is presented for future prospects and research on hydrogen-based energy storage
Quaternary Hydrides Pd1-y-zAgyCuzHx Embedded Atom Method Potentials for Hydrogen Energy Applications
Jan 2021
Publication
The Pd-H system has attracted extensive attention. Pd can absorb considerable amount of H at room temperature this ability is reversible so it is suitable for multiple energy applications. Pd-Ag alloys possess higher H permeability solubility and narrower miscibility gap with better mechanical properties than pure Pd but sulfur poisoning remains an issue. Pd-Cu alloys have excellent resistance to sulfur and carbon monoxide poisoning and hydrogen embrittlement good mechanical properties and broader temperature working environments over pure Pd but relatively lower hydrogen permeability and solubility than pure Pd and Pd-Ag alloys. This suggests that alloying Pd with Ag and Cu to create Pd-Ag-Cu ternary alloys can optimize the overall performance and substantially lowers the cost. Thus in this paper we provide the first embedded atom method potentials for the quaternary hydrides Pd1-y-zAgyCuzHx. The fully analytical potentials are fitted utilizing the central atom method without performing time-consuming molecular dynamics simulations.
A New Design Concept for Prevention of Hydrogen-induced Mechanical Degradation: Viewpoints of Metastability and High Entropy
Dec 2018
Publication
‟How crack growth is prevented” is key to improve both fatigue and monotonic fracture resistances under an influence of hydrogen. Specifically the key points for the crack growth resistance are hydrogen diffusivity and local ductility. For instance type 304 austenitic steels show high hydrogen embrittlement susceptibility because of the high hydrogen diffusivity of bcc (α´) martensite. In contrast metastability in specific austenitic steels enables fcc (γ) to hcp (ε) martensitic transformation which decreases hydrogen diffusivity and increases strength simultaneously. As a result even if hydrogen-assisted cracking occurs during monotonic tensile deformation the ε-martensite acts to arrest micro-damage evolution when the amount of ε-martensite is limited. Thus the formation of ε-martensite can decrease hydrogen embrittlement susceptibility in austenitic steels. However a considerable amount of ε-martensite is required when we attempt to have drastic improvements of work hardening capability and strength level with respect to transformation-induced plasticity effect. Since the hcp structure contains a less number of slip systems than fcc and bcc the less stress accommodation capacity often causes brittle-like failure when the ε-martensite fraction is large. Therefore ductility of ε-martensite is another key when we maximize the positive effect of ε-martensitic transformation. In fact ε-martensite in a high entropy alloy was recently found to be extraordinary ductile. Consequently the metastable high entropy alloys showed low fatigue crack growth rates in a hydrogen atmosphere compared with conventional metastable austenitic steels with α´-martensitic transformation. We here present effects of metastability to ε-phase and configurational entropy on hydrogen-induced mechanical degradation including monotonic tension properties and fatigue crack growth resistance.
Self-sustainable Protonic Ceramic Electrochemical cells Using a Triple Conducting Electrode for Hydrogen and Power Production
Apr 2020
Publication
The protonic ceramic electrochemical cell (PCEC) is an emerging and attractive technology that converts energy between power and hydrogen using solid oxide proton conductors at intermediate temperatures. To achieve efficient electrochemical hydrogen and power production with stable operation highly robust and durable electrodes are urgently desired to facilitate water oxidation and oxygen reduction reactions which are the critical steps for both electrolysis and fuel cell operation especially at reduced temperatures. In this study a triple conducting oxide of PrNi0.5Co0.5O3-δ perovskite is developed as an oxygen electrode presenting superior electrochemical performance at 400~600 °C. More importantly the self-sustainable and reversible operation is successfully demonstrated by converting the generated hydrogen in electrolysis mode to electricity without any hydrogen addition. The excellent electrocatalytic activity is attributed to the considerable proton conduction as confirmed by hydrogen permeation experiment remarkable hydration behavior and computations.
Hydrogen Station Location Planning via Geodesign in Connecticut: Comparing Optimization Models and Structured Stakeholder Collaboration
Nov 2021
Publication
Geodesign is a participatory planning approach in which stakeholders use geographic information systems to develop and vet alternative design scenarios in a collaborative and iterative process. This study is based on a 2019 geodesign workshop in which 17 participants from industry government university and non-profit sectors worked together to design an initial network of hydrogen refueling stations in the Hartford Connecticut metropolitan area. The workshop involved identifying relevant location factors rapid prototyping of station network designs and developing consensus on a final design. The geodesign platform which was designed specifically for facility location problems enables breakout groups to add or delete stations with a simple point-and-click operation view and overlay different map layers compute performance metrics and compare their designs to those of other groups. By using these sources of information and their own expert local knowledge participants recommended six locations for hydrogen refueling stations over two distinct phases of station installation. We quantitatively and qualitatively compared workshop recommendations to solutions of three optimal station location models that have been used to recommend station locations which minimize travel times from stations to population and traffic or maximize trips that can be refueled on origin–destination routes. In a post-workshop survey participants rated the workshop highly for facilitating mutual understanding and information sharing among stakeholders. To our knowledge this workshop represents the first application of geodesign for hydrogen refueling station infrastructure planning.
Safety and Other Considerations in the Development of a Hydrogen Fueling Protocol for Heavy-duty Vehicles
Sep 2021
Publication
Several manufacturers are developing heavy duty (HD) hydrogen stations and vehicles as zeroemissions alternatives to diesel and gasoline. In order to meet customer demands the new technology must be comparable to conventional approaches including safety reliability fueling times and final fill levels. For a large HD vehicle with a storage rated to 70 MPa nominal working pressure the goal to meet liquid fuel parity means providing 100 kg of hydrogen in 10 minutes. This paper summarizes the results to date of the PRHYDE project efforts to define the concepts of HD fueling which thereby lays the groundwork for the development of the safe and effective approach to filling these large vehicles. The project starts by evaluating the impact of several different assumptions such as the availability of static vehicle data (e.g. vehicle tank type and volume) and station data (e.g. expected station precooling capability) but also considers using real time dynamic data (e.g. vehicle tank gas temperature and pressure station gas temperature etc.) for optimisation to achieve safety and efficiency improvements. With this information the vehicle or station can develop multiple maps of fill time versus the hydrogen delivery temperature which are used to determine the speed of fueling. This will also allow the station or vehicle to adjust the rate of fueling as the station pre-cooling levels and other conditions change. The project also examines different steps for future protocol development such as communication of data between the vehicle and station and if the vehicle or station is controlling the fueling.
Ammonia Production from Clean Hydrogen and the Implications for Global Natural Gas Demand
Jan 2023
Publication
Non-energy use of natural gas is gaining importance. Gas used for 183 million tons annual ammonia production represents 4% of total global gas supply. 1.5-degree pathways estimate an ammonia demand growth of 3–4-fold until 2050 as new markets in hydrogen transport shipping and power generation emerge. Ammonia production from hydrogen produced via water electrolysis with renewable power (green ammonia) and from natural gas with CO2 storage (blue ammonia) is gaining attention due to the potential role of ammonia in decarbonizing energy value chains and aiding nations in achieving their net-zero targets. This study assesses the technical and economic viability of different routes of ammonia production with an emphasis on a systems level perspective and related process integration. Additional cost reductions may be driven by optimum sizing of renewable power capacity reducing losses in the value chain technology learning and scale-up reducing risk and a lower cost of capital. Developing certification and standards will be necessary to ascertain the extent of greenhouse gas emissions throughout the supply chain as well as improving the enabling conditions including innovative finance and de-risking for facilitating international trade market creation and large-scale project development.
Ignition of Hydrogen-air Mixtures Under Volumetric Expansion Conditions
Sep 2017
Publication
A better understanding of chemical kinetics under volumetric expansion is important for a number of situations relevant to industrial safety including detonation diffraction and direct initiation reflected shock-ignition at obstacles ignition behind a decaying shock among others. The ignition of stoichiometric hydrogen-air mixtures was studied using 0D numerical simulations with time-dependent specific volume variations. The competition between chemical energy release and expansion-induced cooling was characterized for different cooling rates and mathematical forms describing the shock decay rate. The critical conditions for reaction quenching were systematically determined and the thermo-chemistry dynamics were analyzed near the critical conditions.
Electrolyzers Enhancing Flexibility in Electric Grids
Nov 2017
Publication
This paper presents a real-time simulation with a hardware-in-the-loop (HIL)-based approach for verifying the performance of electrolyzer systems in providing grid support. Hydrogen refueling stations may use electrolyzer systems to generate hydrogen and are proposed to have the potential of becoming smarter loads that can proactively provide grid services. On the basis of experimental findings electrolyzer systems with balance of plant are observed to have a high level of controllability and hence can add flexibility to the grid from the demand side. A generic front end controller (FEC) is proposed which enables an optimal operation of the load on the basis of market and grid conditions. This controller has been simulated and tested in a real-time environment with electrolyzer hardware for a performance assessment. It can optimize the operation of electrolyzer systems on the basis of the information collected by a communication module. Real-time simulation tests are performed to verify the performance of the FEC-driven electrolyzers to provide grid support that enables flexibility greater economic revenue and grid support for hydrogen producers under dynamic conditions. The FEC proposed in this paper is tested with electrolyzers however it is proposed as a generic control topology that is applicable to any load.
Fracture Properties of Welded 304L in Hydrogen Environments
Sep 2021
Publication
Austenitic stainless steels are used for hydrogen containment of high-pressure hydrogen gas due to their ability to retain high fracture properties despite the degradation due to hydrogen. Forging and other strain-hardening processes are desirable for austenitic stainless steels to increase the material strength and thus accommodate higher stresses and reduce material costs. Welding is often necessary for assembling components but it represents an area of concern in pressure containment structures due to the potential for defects more environmentally susceptible microstructure and reduced strength. Electron beam (EB) welding represent an advanced joining process which has advantages over traditional arc welding techniques through reduced input heat and reduced heat-affected zone (HAZ) microstructure and thus present a means to maintain high strength and improve weld performance in hydrogen gas containment. In this study fracture coupons were extracted from EB welds in forged 304L and subjected to thermal gaseous hydrogen precharging at select pressures to introduce different levels of internal hydrogen content. Fracture tests were then performed on hydrogen precharged coupons at temperatures of both 293 K and 223 K. It was observed that fracture resistance (JH) was dependent on internal hydrogen concentration; higher hydrogen concentrations resulted in lower fracture resistance in both the forged 304L base material and the 304L EB welds. This trend was also apparent at both temperatures: 293 K and 223 K. EB weld samples however maintain high fracture resistance comparable to the forged 304L base material. The role of weld microstructure solidification on fracture is discussed.
Everything About Hydrogen Podcast: What's Brewing in the UK Clean Hydrogen Sector?
Dec 2021
Publication
Chris Jackson is the Founder and CEO of Protium Green Solutions based in London. Protium is a hydrogen energy services company that designs develops finances owns and operates clean hydrogen solutions for clients to achieve net zero energy emissions at their industrial/manufacturing sites. Chris will talk to us about the Protium story and also give us some insight into a major project that Protium recently announced in conjunction Budweiser Brewing Group UK&Ireland to explore the deployment of zero emission green hydrogen at Magor brewery in South Wales one of the largest breweries in the UK. To that end in order to get the full story about this project we are delighted to say that we have yet another great guest on this episode. Tom Brewer who leads Global Environmental Sustainability efforts at AB InBev the parent company of Budweiser Brewing Group will join us for the final segment of the show to talk about how hydrogen fits into AB InBev’s vision of a sustainable future for the company.
The podcast can be found on their website
The podcast can be found on their website
Study of the Microstructural and First Hydrogenation Properties of TiFe Alloy with Zr, Mn and V as Additives
Jul 2021
Publication
In this paper we report the effect of adding Zr + V or Zr + V + Mn to TiFe alloy on microstructure and hydrogen storage properties. The addition of only V was not enough to produce a minimum amount of secondary phase and therefore the first hydrogenation at room temperature under a hydrogen pressure of 20 bars was impossible. When 2 wt.% Zr + 2 wt.% V or 2 wt.% Zr + 2 wt.% V + 2 wt.% Mn is added to TiFe the alloy shows a finely distributed Ti2Fe-like secondary phase. These alloys presented a fast first hydrogenation and a high capacity. The rate-limiting step was found to be 3D growth diffusion controlled with decreasing interface velocity. This is consistent with the hypothesis that the fast reaction is likely to be the presence of Ti2Fe-like secondary phases that act as a gateway for hydrogen.
On the Climate Impacts of Blue Hydrogen Production
Nov 2021
Publication
Natural gas based hydrogen production with carbon capture and storage is referred to as blue hydrogen. If substantial amounts of CO2 from natural gas reforming are captured and permanently stored such hydrogen could be a low-carbon energy carrier. However recent research raises questions about the effective climate impacts of blue hydrogen from a life cycle perspective. Our analysis sheds light on the relevant issues and provides a balanced perspective on the impacts on climate change associated with blue hydrogen. We show that such impacts may indeed vary over large ranges and depend on only a few key parameters: the methane emission rate of the natural gas supply chain the CO2 removal rate at the hydrogen production plant and the global warming metric applied. State-of-the-art reforming with high CO2 capture rates combined with natural gas supply featuring low methane emissions does indeed allow for substantial reduction of greenhouse gas emissions compared to both conventional natural gas reforming and direct combustion of natural gas. Under such conditions blue hydrogen is compatible with low-carbon economies and exhibits climate change impacts at the upper end of the range of those caused by hydrogen production from renewable-based electricity. However neither current blue nor green hydrogen production pathways render fully “net-zero” hydrogen without additional CO2 removal.
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