Switzerland
Metal Hydroborates: From Hydrogen Stores to Solid Electrolyte
Nov 2021
Publication
The last twenty years of an intense research on metal hydroborates as solid hydrogen stores and solid electrolytes are reviewed. It is shown that from the most promising application in hydrogen storage due to their high gravimetric and volumetric capacities the focus has moved to solid electrolytes due to high cation mobility in disordered structures with rotating or tumbling anions-hydroborate clusters. Various strategies of overcoming the strong covalent bonding of hydrogen in hydroborates for hydrogen storage and disordering their structures at room temperature for solid electrolytes are discussed. The important role of crystal chemistry and crystallography knowledge in material design can be read in the cited literature.
Materials for Hydrogen Storage
Aug 2003
Publication
Hydrogen storage is a materials science challenge because for all six storage methods currently being investigated materials with either a strong interaction with hydrogen or without any reaction are needed. Besides conventional storage methods i.e. high pressure gas cylinders and liquid hydrogen the physisorption of hydrogen on materials with a high specific surface area hydrogen intercalation in metals and complex hydrides and storage of hydrogen based on metals and water are reviewed.
Molecular Transport Effects of Hydrocarbon Addition on Turbulent Hydrogen Flame Propagation
Sep 2007
Publication
We analytically investigated the influence of light hydrocarbons on turbulent premixed H2/air atmospheric flames under lean conditions in view of safe handling of H2 systems applications in H2 powered IC engines and gas turbines and also with an orientation towards modelling of H2 combustion. For this purpose an algebraic flame surface wrinkling model included with pressure and fuel type effects is used. The model predictions of turbulent premixed flames are compared with the set of corresponding experimental data of Kido et al. (Kido Nakahara et al. 2002). These expanding spherical flame data include H2–air mixtures doped with CH4 and C3H8 while the overall equivalence ratio of all the fuel/air mixtures is fixed at 0.8 for constant unstretched laminar flame speed of 25 cm/s by varying N2 composition. The model predictions show that there is little variation in turbulent flame speed ST for C3H8 additions up to 20-vol%. However for 50 vol% doping flame speed decreases by as much as 30 % from 250 cm/s that of pure H2–air mixtures for turbulence intensity of 200 cm/s. With respect to CH4 for 50 vol% doping ST reduces by only 6 % cf. pure H2/air mixture. In the first instance the substantial decrease of ST with C3H8 addition may be attributed to the increase in the Lewis number of the dual-fuel mixture and proportional restriction of molecular mobility of H2. That is this decrease in flame speed can be explained using the concept of leading edges of the turbulent flame brush (Lipatnikov and Chomiak 2005). As these leading edges have mostly positive curvature (convex to the unburned side) preferential-diffusive-thermal instabilities cause recognizable impact on flame speed at higher levels of turbulence with the effect being very strong for lean H2 mixtures. The lighter hydrocarbon substitutions tend to suppress the leading flame edges and possibly transition to detonation in confined structures and promote flame front stability of lean turbulent premixed flames. Thus there is a necessity to develop a predictive reaction model to quantitatively show the strong influence of molecular transport coefficients on ST.
Comparative Life Cycle Assessment of Hydrogen-fuelled Passenger Cars
Feb 2021
Publication
In order to achieve gradual but timely decarbonisation of the transport sector it is essential to evaluate which types of vehicles provide a suitable environmental performance while allowing the use of hydrogen as a fuel. This work compares the environmental life-cycle performance of three different passenger cars fuelled by hydrogen: a fuel cell electric vehicle an internal combustion engine car and a hybrid electric vehicle. Besides two vehicles that use hydrogen in a mixture with natural gas or gasoline were considered. In all cases hydrogen produced by wind power electrolysis was assumed. The resultant life-cycle profiles were benchmarked against those of a compressed natural gas car and a hybrid electric vehicle fed with natural gas. Vehicle infrastructure was identified as the main source of environmental burdens. Nevertheless the three pure hydrogen vehicles were all found to be excellent decarbonisation solutions whereas vehicles that use hydrogen mixed with natural gas or gasoline represent good opportunities to encourage the use of hydrogen in the short term while reducing emissions compared to ordinary vehicles.
Measurement Challenges for Hydrogen Vehicles
Apr 2019
Publication
Uptake of hydrogen vehicles is an ideal solution for countries that face challenging targets for carbon dioxide reduction. The advantage of hydrogen fuel cell electric vehicles is that they behave in a very similar way to petrol engines yet they do not emit any carbon containing products during operation. The hydrogen industry currently faces the dilemma that they must meet certain measurement requirements (set by European legislation) but cannot do so due to a lack of available methods and standards. This paper outlines the four biggest measurement challenges that are faced by the hydrogen industry including flow metering quality assurance quality control and sampling.
Dynamic System Modeling of Thermally-integrated Concentrated PV-electrolysis
Feb 2021
Publication
Understanding the dynamic response of a solar fuel processing system utilizing concentrated solar radiation and made of a thermally-integrated photovoltaic (PV) and water electrolyzer (EC) is important for the design development and implementation of this technology. A detailed dynamic non-linear process model is introduced for the fundamental system components (i.e. PV EC pump etc.) in order to investigate the coupled system behavior and performance synergy notably arising from the thermal integration. The nominal hydrogen production power is ∼2 kW at a hydrogen system efficiency of 16–21% considering a high performance triple junction III-V PV module and a proton exchange membrane EC. The device operating point relative to the maximum power point of the PV was shown to have a differing influence on the system performance when subject to temperature changes. The non-linear coupled behavior was characterised in response to step changes in water flowrate and solar irradiance and hysteresis of the current-voltage operating point was demonstrated. Whilst the system responds thermally to changes in operating conditions in the range of 0.5–2 min which leads to advantageously short start-up times a number of control challenges are identified such as the impact of pump failure electrical PV-EC disconnection and the potentially damaging accentuated temperature rise at lower water flowrates. Finally the simulation of co-generation of heat and hydrogen for various operating conditions demonstrates the significant potential for system efficiency enhancements and the required development of control strategies for demand matching is discussed.
Seasonal Energy Storage in Aluminium for 100 Percent Solar Heat and Electricity Supply
Sep 2019
Publication
In order to reduce anthropogenic global warming governments around the world have decided to reduce CO2 emissions from fossil fuels dramatically within the next decades. In moderate and cold climates large amounts of fossil fuels are used for space heating and domestic hot water production in winter. Although on an annual base solar energy is available in large quantities in these regions least of the solar resource is available in winter when most of the energy is needed. Therefore solutions are needed to store and transfer renewable energy from summer to winter. In this paper a seasonal energy storage based on the aluminium redox cycle (Al3+→Al→ Al3+) is proposed. For charging electricity from solar or other renewable sources is used to convert aluminium oxide or aluminium hydroxide to elementary aluminium (Al3+→Al). In the discharging process aluminium is oxidized (Al→Al3+) releasing hydrogen heat and aluminium hydroxide or aluminium oxide as a by-product. Hydrogen is used in a fuel cell to produce electricity. Heat produced from the aluminium oxidation process and by the fuel cell is used for domestic hot water production and space heating. The chemical reactions and energy balances are presented and simulation results are shown for a system that covers the entire energy demand for electricity space heating and domestic hot water of a new multi-family building with rooftop photovoltaic energy in combination with the seasonal Al energy storage cycle. It shows that 7–11 kWp of photovoltaic installations and 350–530 kg Al would be needed per apartment for different Swiss climates. Environmental life cycle data shows that the global warming potential and non-renewable primary energy consumption can be reduced significantly compared to today's common practice of heating with natural gas and using electricity from the ENTSO-E network. The presumptive cost were estimated and indicate a possible cost-competitiveness for this system in the near future.
Combined Hydrogen Production and Electricity Storage using a Vanadium Manganese Redox Dual-flow Battery
Aug 2021
Publication
A redox dual-flow battery is distinct from a traditional redox flow battery (RFB) in that the former includes a secondary energy platform in which the pre-charged electrolytes can be discharged in external catalytic reactors through decoupled redox-mediated hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The concept offers several advantages over conventional electrolysis in terms of safety durability modularity and purity. In this work we demonstrate a vanadium-manganese redox-flow battery in which Mn3+/Mn2+ and V3+/V2+ respectively mediate the OER and the HER in Mo2C-based and RuO2-based catalysts. The flow battery demonstrates an average energy efficiency of 68% at a current density of 50 mA ⋅ cm−2 (cell voltage = 1.92 V) and a relative energy density 45% higher than the conventional all-vanadium RFB. Both electrolytes are spontaneously discharged through redox-mediated HER and OER with a faradic efficiency close to 100%.
Hydrogen Production from Natural Gas and Biomethane with Carbon Capture and Storage – A Techno-environmental Analysis
Mar 2020
Publication
This study presents an integrated techno-environmental assessment of hydrogen production from natural gas and biomethane combined with CO2 capture and storage (CCS). We have included steam methane reforming (SMR) and autothermal reforming (ATR) for syngas production. CO2 is captured from the syngas with a novel vacuum pressure swing adsorption (VPSA) process that combines hydrogen purification and CO2 separation in one cycle. As comparison we have included cases with conventional amine-based technology. We have extended standard attributional Life Cycle Assessment (LCA) following ISO standards with a detailed carbon balance of the biogas production process (via digestion) and its by-products. The results show that the life-cycle greenhouse gas (GHG) performance of the VPSA and amine-based CO2 capture technologies is very similar as a result of comparable energy consumption. The configuration with the highest plant-wide CO2 capture rate (almost 100% of produced CO2 captured) is autothermal reforming with a two-stage water-gas shift and VPSA CO2 capture – because the latter has an inherently high CO2 capture rate of 98% or more for the investigated syngas. Depending on the configuration the addition of CCS to natural gas reforming-based hydrogen production reduces its life-cycle Global Warming Potential by 45–85 percent while the other environmental life-cycle impacts slightly increase. This brings natural gas-based hydrogen on par with renewable electricity-based hydrogen regarding impacts on climate change. When biomethane is used instead of natural gas our study shows potential for net negative greenhouse gas emissions i.e. the net removal of CO2 over the life cycle of biowaste-based hydrogen production. In the special case where the biogas digestate is used as agricultural fertiliser and where a substantial amount of the carbon in the digestate remains in the soil the biowaste-based hydrogen reaches net-negative life cycle greenhouse gas emissions even without the application of CCS. Addition of CCS to biomethane-based hydrogen production leads to net-negative emissions in all investigated cases.
Evaluation of Sorbents for High Temperature Removal of Tars, Hydrogen Sulphide, Hydrogen Chloride and Ammonia from Biomass-derived Syngas by Using Aspen Plus
Jan 2020
Publication
Biomass gasification is a promising technology to produce secondary fuels or heat and power offering considerable advantages over fossil fuels. An important aspect in the usage of producer gas is the removal of harmful contaminants from the raw syngas. Thus the object of this study is the development of a simulation model for a gasifier including gas clean-up for which a fluidized-bed gasifier for biomass-derived syngas production was considered based on a quasi-equilibrium approach through Gibbs free energy minimisation and including an innovative hot gas cleaning constituted by a combination of catalyst sorbents inside the gasification reactor catalysts in the freeboard and subsequent sorbent reactors by using Aspen Plus software. The gas cleaning chain simulates the raw syngas clean-up for several organic and inorganic contaminants i.e. toluene benzene naphthalene hydrogen sulphide hydrogen chloride and ammonia. The tar and inorganic contaminants final values achieved are under 1 g/Nm3 and 1 ppm respectively.
Magnetic Field Enhancement of Electrochemical Hydrogen Evolution Reaction Probed by Magneto-optics
Nov 2020
Publication
External magnetic fields affect various electrochemical processes and can be used to enhance the efficiency of the electrochemical water splitting reaction. However the driving forces behind this effect are poorly understood due to the analytical challenges of the available interface-sensitive techniques. Here we present a set-up based on magneto- and electro-optical probing which allows to juxtapose the magnetic properties of the electrode with the electrochemical current densities in situ at various applied potentials and magnetic fields. On the example of an archetypal hydrogen evolution catalyst Pt (in a form of Co/Pt superlattice) we provide evidence that a magnetic field acts on the electrochemical double layer affecting the local concentration gradient of hydroxide ions which simultaneously affects the magneto-optical and magnetocurrent response.
Environmental Degradation Effect of High-Temperature Water and Hydrogen on the Fracture Behavior of Low-Alloy Reactor Pressure Vessel Steels
Dec 2019
Publication
Structural integrity of reactor pressure vessel (RPV) in light water reactors (LWR) is of highest importance regarding operation safety and lifetime. The fracture behaviour of low-alloy RPV steels with different dynamic strain aging (DSA) & environmental assisted cracking (EAC) susceptibilities in simulated LWR environments was evaluated by elastic plastic fracture mechanics tests (EPFM) and by metallo- and fractographic post-test analysis. Exposure to high temperature water (HTW) environments at LWR temperatures revealed only moderated reductions in the fracture initiation and tearing resistance of low alloy RPV steels with high DSA or EAC susceptibility accompanied with a moderate but clear change in fracture morphology which indicates the potential synergies of hydrogen/HTW embrittlement with DSA and EAC under suitable conditions. The most pronounced degradation effects occurred in a) RPV steels with high DSA susceptibility where the fracture initiation and tearing resistance reduction increased with decreasing loading rate and were most pronounced in hydrogenated HTW and b) high sulphur steels with high EAC susceptibility in aggressive occluded crevice environment and with preceding fast EAC crack growth in oxygenated HTW. The moderate effects are due to the low hydrogen availability in HTW together with high density of fine-dispersed hydrogen traps in RPV steels. Stable ductile transgranular tearing by microvoid coalescence was the dominant failure mechanism in all environments with additional varying few % of secondary cracks macrovoids and quasi-cleavage in HTW. The observed behavior suggests a combination of plastic strain localisation by the Hydrogen-enhanced Local Plasticity (HELP) mechanism in synergy with DSA and Hydrogen-enhanced Strain-induced Vacancies (HESIV) mechanism with additional minor contributions of Hydrogen-enhanced Decohesion Embrittlement (HEDE) mechanism.
Balancing Wind-power Fluctuation Via Onsite Storage Under Uncertainty Power-to-hydrogen-to-power Versus Lithium Battery
Oct 2019
Publication
Imbalance costs caused by forecasting errors are considerable for grid-connected wind farms. In order to reduce such costs two onsite storage technologies i.e. power-to-hydrogen-to-power and lithium battery are investigated considering 14 uncertain technological and economic parameters. Probability density distributions of wind forecasting errors and power level are first considered to quantify the imbalance and excess wind power. Then robust optimal sizing of the onsite storage is performed under uncertainty to maximize wind-farm profit (the net present value). Global sensitivity analysis is further carried out for parameters prioritization to highlight the key influential parameters. The results show that the profit of power-to-hydrogen-to-power case is sensitive to the hydrogen price wind forecasting accuracy and hydrogen storage price. When hydrogen price ranges in (2 6) €/kg installing only electrolyzer can earn profits over 100 k€/MWWP in 9% scenarios with capacity below 250 kW/MWWP under high hydrogen price (over 4 €/kg); while installing only fuel cell can achieve such high profits only in 1.3% scenarios with capacity below 180 kW/MWWP. Installing both electrolyzer and fuel cell (only suggested in 22% scenarios) results in profits below 160 k€/MWWP and particularly 20% scenarios allow for a profit below 50 k€/MWWP due to the contradictory effects of wind forecasting error hydrogen and electricity price. For lithium battery investment cost is the single highly influential factor which should be reduced to 760 €/kWh. The battery capacity is limited to 88 kW h/MWWP. For profits over 100 k€/MWWP (in 3% scenarios) the battery should be with an investment cost below 510 €/kWh and a depth of discharge over 63%. The power-to-hydrogen-to-power case is more advantageous in terms of profitability reliability and utilization factor (full-load operating hours) while lithium battery is more helpful to reduce the lost wind and has less environmental impact considering current hydrogen market.
Hydrogen: The Future Energy Carrier
Jul 2010
Publication
Since the beginning of the twenty-first century the limitations of the fossil age with regard to the continuing growth of energy demand the peaking mining rate of oil the growing impact of CO2 emissions on the environment and the dependency of the economy in the industrialized world on the availability of fossil fuels became very obvious. A major change in the energy economy from fossil energy carriers to renewable energy fluxes is necessary. The main challenge is to efficiently convert renewable energy into electricity and the storage of electricity or the production of a synthetic fuel. Hydrogen is produced from water by electricity through an electrolyser. The storage of hydrogen in its molecular or atomic form is a materials challenge. Some hydrides are known to exhibit a hydrogen density comparable to oil; however these hydrides require a sophisticated storage system. The system energy density is significantly smaller than the energy density of fossil fuels. An interesting alternative to the direct storage of hydrogen are synthetic hydrocarbons produced from hydrogen and CO2 extracted from the atmosphere. They are CO2 neutral and stored like fossil fuels. Conventional combustion engines and turbines can be used in order to convert the stored energy into work and heat.
Link to document download on Royal Society Website
Link to document download on Royal Society Website
Seasonal Energy Storage for Zero-emissions Multi-energy Systems Via Underground Hydrogen Storage
Jan 2020
Publication
The deployment of diverse energy storage technologies with the combination of daily weekly and seasonal storage dynamics allows for the reduction of carbon dioxide (CO2) emissions per unit energy provided. In particular the production storage and re-utilization of hydrogen starting from renewable energy has proven to be one of the most promising solutions for offsetting seasonal mismatch between energy generation and consumption. A realistic possibility for large-scale hydrogen storage suitable for long-term storage dynamics is presented by salt caverns. In this contribution we provide a framework for modelling underground hydrogen storage with a focus on salt caverns and we evaluate its potential for reducing the CO2 emissions within an integrated energy systems context. To this end we develop a first-principle model which accounts for the transport phenomena within the rock and describes the dynamics of the stored energy when injecting and withdrawing hydrogen. Then we derive a linear reduced order model that can be used for mixed-integer linear program optimization while retaining an accurate description of the storage dynamics under a variety of operating conditions. Using this new framework we determine the minimum-emissions design and operation of a multi-energy system with H2 storage. Ultimately we assess the potential of hydrogen storage for reducing CO2 emissions when different capacities for renewable energy production and energy storage are available mapping emissions regions on a plane defined by storage capacity and renewable generation. We extend the analysis for solar- and wind-based energy generation and for different energy demands representing typical profiles of electrical and thermal demands and different CO2 emissions associated with the electric grid.
Enabling Low-carbon Hydrogen Supply Chains Through Use of Biomass and Carbon Capture and Storage: A Swiss Case Study
Jul 2020
Publication
This study investigates the optimal design of low-carbon hydrogen supply chains on a national scale. We consider hydrogen production based on several feedstocks and energy sources namely water with electricity natural gas and biomass. When using natural gas we couple hydrogen production with carbon capture and storage. The design of the hydrogen biomass and carbon dioxide (CO2 ) infrastructure is performed by solving an optimization problem that determines the optimal selection size and location of the hydrogen production technologies and the optimal structure of the hydrogen biomass and CO2 O2 networks. First we investigate the rationale behind the optimal design of low-carbon hydrogen supply chains by referring to an idealized system configuration and by performing a parametric analysis of the most relevant design parameters of the supply chains such as biomass availability. This allows drawing general conclusions independent of any specific geographic features about the minimum-cost and minimum-emissions system designs and network structures. Moreover we analyze the Swiss case study to derive specific guidelines concerning the design of hydrogen supply chains deploying carbon capture and storage. We assess the impact of relevant design parameters such as location of CO2 storage facilities techno-economic features of CO2 capture technologies and network losses on the optimal supply chain design and on the competition between the hydrogen and CO2 networks. Findings highlight the fundamental role of biomass (when available) and of carbon capture and storage for decarbonizing hydrogen supply chains while transitioning to a wider deployment of renewable energy sources.
A New Technology for Hydrogen Safety: Glass Structures as a Storage System
Sep 2011
Publication
The storage of hydrogen poses inherent weight volume and safety obstacles. An innovative technology which allows for the storage of hydrogen in thin sealed glass capillaries ensures the safe infusion storage and controlled release of hydrogen gas under pressures up to 100 MPa. Glass is a non-flammable material which also guarantees high burst pressures. The pressure resistance of single and multiple capillaries has been determined for different glass materials. Borosilicate capillaries have been proven to have the highest pressure resistance and have therefore been selected for further series of advanced testing. The innovative storage system is finally composed of a variable number of modules. As such in the case of the release of hydrogen this modular arrangement allows potential hazards to be reduced to a minimum. Further advantage of a modular system is the arrangement of single modules in every shape and volume dependent on the final application. Therefore the typical locations of storage systems e.g. the rear of cars can be modified or shifted to places of higher safety and not directly involved in crashes. The various methods of refilling and releasing capillaries with compressed hydrogen the increase of burst pressures through pre-treatment as well as the theoretical analysis and experimental results of the resistance of glass capillaries will further be discussed in detail.
A Manganese Hydride Molecular Sieve for Practical Hydrogen Storage Under Ambient Conditions
Dec 2018
Publication
A viable hydrogen economy has thus far been hampered by the lack of an inexpensive and convenient hydrogen storage solution meeting all requirements especially in the areas of long hauls and delivery infrastructure. Current approaches require high pressure and/or complex heat management systems to achieve acceptable storage densities. Herein we present a manganese hydride molecular sieve that can be readily synthesized from inexpensive precursors and demonstrates a reversible excess adsorption performance of 10.5 wt% and 197 kgH2 m-3 at 120 bar at ambient temperature with no loss of activity after 54 cycles. Inelastic neutron scattering and computational studies confirm Kubas binding as the principal mechanism. The thermodynamically neutral adsorption process allows for a simple system without the need for heat management using moderate pressure as a toggle. A storage material with these properties will allow the DOE system targets for storage and delivery to be achieved providing a practical alternative to incumbents such as 700 bar systems which generally provide volumetric storage values of 40 kgH2 m-3 or less while retaining advantages over batteries such as fill time and energy density. Reasonable estimates for production costs and loss of performance due to system implementation project total energy storage costs roughly 5 times cheaper than those for 700 bar tanks potentially opening doors for increased adoption of hydrogen as an energy vector.
Feasibility of Renewable Hydrogen Based Energy Supply for a District
Sep 2017
Publication
Renewable generation technologies (e.g. photovoltaic panels (PV)) are often installed in buildings and districts with an aim to decrease their carbon emissions and consumption of non-renewable energy. However due to a mismatch between supply and demand at an hourly but also on a seasonal timescale; a large amount of electricity is exported to the grid rather than used to offset local demand. A solution to this is local storage of electricity for subsequent self-consumption. This could additionally provide districts with new business opportunities financial stability flexibility and reliability.<br/>In this paper the feasibility of hydrogen based electricity storage for a district is evaluated. The district energy system (DES) includes PV and hybrid photovoltaic panels (PVT). The proposed storage system consists of production of hydrogen using the renewable electricity generated within the district hydrogen storage and subsequent use in a fuel cell. Combination of battery storage along with hydrogen conversion and storage is also evaluated. A multi-energy optimization approach is used to model the DES. Results of the model are optimal battery capacity electrolyzer capacity hydrogen storage capacity fuel cell capacity and energy flows through the system. The model is also used to compare different system design configurations. The results of this analysis show that both battery capacity and conversion of electricity to hydrogen enable the district to decrease its carbon emissions by approximately 22% when compared to the reference case with no energy storage.
Towards Climate Resilient Urban Energy Systems: A Review
Jun 2020
Publication
Climate change and increased urban population are two major concerns for society. Moving towards more sustainable energy solutions in the urban context by integrating renewable energy technologies supports decarbonizing the energy sector and climate change mitigation. A successful transition also needs adequate consideration of climate change including extreme events to ensure the reliable performance of energy systems in the long run. This review provides an overview of and insight into the progress achieved in the energy sector to adapt to climate change focusing on the climate resilience of urban energy systems. The state-of-the-art methodology to assess impacts of climate change including extreme events and uncertainties on the design and performance of energy systems is described and discussed. Climate resilience is an emerging concept that is increasingly used to represent the durability and stable performance of energy systems against extreme climate events. However it has not yet been adequately explored and widely used as its definition has not been clearly articulated and assessment is mostly based on qualitative aspects. This study reveals that a major limitation in the state-of-the-art is the inadequacy of climate change adaptation approaches in designing and preparing urban energy systems to satisfactorily address plausible extreme climate events. Furthermore the complexity of the climate and energy models and the mismatch between their temporal and spatial resolutions are the major limitations in linking these models. Therefore few studies have focused on the design and operation of urban energy infrastructure in terms of climate resilience. Considering the occurrence of extreme climate events and increasing demand for implementing climate adaptation strategies the study highlights the importance of improving energy system models to consider future climate variations including extreme events to identify climate resilient energy transition pathways.
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