The fraction of tritium converted to the water form in a fire scenario is one of the metrics of greatest interest for radiological safety assessments. The conversion fraction is one of the prime variables contributing to the hazard assessment. This paper presents measurements of oxidation rates for the non-radioactive hydrogen isotopes (protium and deuterium) at sub-flammable concentrations that are typical of many of the most likely tritium release scenarios. These measurements are fit to a simplified 1-step kinetic rate expression, and the isotopic trends for protium and deuterium are extrapolated to produce a model appropriate for tritium. The effects of the new kinetic models are evaluated via CFD simulations of an ISO-9705 standard room fire that includes a trace release of hydrogen isotope (tritium), illustrating the high importance of the correct (measurement-based) kinetics to the outcome of the simulated conversion.
Ignition of a flammable tritium-air mixture is the most probable means to produce the water form (T2O or HTO), which is more easily absorbed by living tissue and is hence ~10,000 times more hazardous to human health when uptake occurs compared to the gaseous form (T2 or HT; per Mishima and Steele, 2002). Tritium-air mixtures with T2 concentrations below 4 mol% are considered sub-flammable and will not readily convert to the more hazardous water form. It is therefore desirable from a safety perspective to understand the dispersion behavior of tritium under different release conditions, especially since tritium is often stored in quantities and pressures much lower than is typical for normal hydrogen. The formation of a flammable layer at the ceiling is a scenario of particular concern because the rate of dispersion to nonflammable conditions is slowest in this configuration, which maximizes the time window over which the flammable tritium may encounter an ignition source. This report describes the processes of buoyant rise and dispersion of tritium. Accumulation of flammable concentrations of tritium next to the ceiling is a common safety concern for hydrogen, but this situation can only occur if dispersion rates are slow with respect to rates of release and rise. Theory and simulations demonstrate that buoyancy does not cause regions with flammable concentrations to form within buildings from sources that have previously been mixed to sub-flammable concentrations. A simulated series of tritium release events with their associated dispersion behavior are reported herein; these simulations apply computational fluid dynamics to rooms with three different ceiling heights and a variety of tritium release rates. Safety related quantities from these simulations are reported, including the mass and volume of tritium occurring in a flammable mixture, the presence or absence of a flammable layer at the ceiling, and the time required for dispersion to nonflammable conditions after the end of the tritium release event. These safety metrics are influenced by the magnitude and rate of the tritium release with respect to the air volume in the room and also the momentum of the plume or jet with respect to the ceiling height. Several screening criteria are recommended to assess whether a specific tritium release scenario is likely to form a flammable layer at the ceiling. The methods and results in this modeling study have applicability to explosion safety analysis for other buoyant flammable gases, including the lighter isotopes of hydrogen.
Two relatively under-reported facets of fuel storage fire safety are examined in this work for a 250, 000 gallon two-tank storage system. Ignition probability is linked to the radiative flux from a presumed fire. First, based on observed features of existing designs, fires are expected to be largely contained within a designed footprint that will hold the full spilled contents of the fuel. The influence of the walls and the shape of the tanks on the magnitude of the fire is not a well-described aspect of conventional fire safety assessment utilities. Various resources are herein used to explore the potential hazard for a contained fire of this nature. Second, an explosive attack on the fuel storage has not been widely considered in prior work. This work explores some options for assessing this hazard. The various methods for assessing the constrained conventional fires are found to be within a reasonable degree of agreement. This agreement contrasts with the hazard from an explosive dispersal. Best available assessment techniques are used, which highlight some inadequacies in the existing toolsets for making predictions of this nature. This analysis, using the best available tools, suggests the offset distance for the ignition hazard from a fireball will be on the same order as the offset distance for the blast damage. This suggests the buy-down of risk by considering the fireball is minimal when considering the blast hazards. Assessment tools for the fireball predictions are not particularly mature, and ways to improve them for a higher-fidelity estimate are noted.
Two relatively under-reported facets of fuel storage fire safety are examined in this work for a 250, 000 gallon two-tank storage system. Ignition probability is linked to the radiative flux from a presumed fire. First, based on observed features of existing designs, fires are expected to be largely contained within a designed footprint that will hold the full spilled contents of the fuel. The influence of the walls and the shape of the tanks on the magnitude of the fire is not a well-described aspect of conventional fire safety assessment utilities. Various resources are herein used to explore the potential hazard for a contained fire of this nature. Second, an explosive attack on the fuel storage has not been widely considered in prior work. This work explores some options for assessing this hazard. The various methods for assessing the constrained conventional fires are found to be within a reasonable degree of agreement. This agreement contrasts with the hazard from an explosive dispersal. Best available assessment techniques are used, which highlight some inadequacies in the existing toolsets for making predictions of this nature. This analysis, using the best available tools, suggests the offset distance for the ignition hazard from a fireball will be on the same order as the offset distance for the blast damage. This suggests the buy-down of risk by considering the fireball is minimal when considering the blast hazards. Assessment tools for the fireball predictions are not particularly mature, and ways to improve them for a higher-fidelity estimate are noted.
We study the point-by-point inscription of sapphire parallel fiber Bragg gratings (sapphire pFBGs) in a fully multimode system. A parallel FBG is shown to be critical in enabling detectable and reliable high-order grating signals. The impacts of modal volume, spatial coherence, and grating location on reflectivity are examined. Three cascaded seventh-order pFBGs are fabricated in one sapphire fiber for wavelength multiplexed temperature sensing. Using a low-cost, fully multimode 850-nm interrogator, reliable measurement up to 1500°C is demonstrated.
This is the Sandia report from a joint NSRD project between Sandia National Labs and Savannah River National Labs. The project involved development of simulation tools and data intended to be useful for tritium operations safety assessment. Tritium is a synthetic isotope of hydrogen that has a limited lifetime, and it is found at many tritium facilities in the form of elemental gas (T2). The most serious risk of reasonable probability in an accident scenario is when the tritium is released and reacts with oxygen to form a water molecule, which is subsequently absorbed into the human body. This tritium oxide is more readily absorbed by the body and therefore represents a limiting factor for safety analysis. The abnormal condition of a fire may result in conversion of the safer T2 inventory to the more hazardous oxidized form. It is this risk that tends to govern the safety protocols. Tritium fire datasets do not exist, so prescriptive safety guidance is largely conservative and reliant on means other than testing to formulate guidelines. This can have a consequence in terms of expensive and/or unnecessary mitigation design, handling protocols, and operational activities. This issue can be addressed through added studies on the behavior of tritium under representative conditions. Due to the hazards associated with the tests, this is being approached mainly from a modeling and simulation standpoint and surrogate testing. This study largely establishes the capability to generate simulation predictions with sufficiently credible characteristics to be accepted for safety guidelines as a surrogate for actual data through a variety of testing and modeling activities.
In accident scenarios involving release of tritium during handling and storage, the level of risk to human health is dominated by the extent to which radioactive tritium is oxidized to the water form (T2O or THO). At some facilities, tritium inventories consist of very small quantities stored at sub-atmospheric pressure, which means that tritium release accident scenarios will likely produce concentrations in air that are well below the lower flammability limit. It is known that isotope effects on reaction rates should result in slower oxidation rates for heavier isotopes of hydrogen, but this effect has not previously been quantified for oxidation at concentrations well below the lower flammability limit for hydrogen. This work describes hydrogen isotope oxidation measurements in an atmospheric tube furnace reactor. These measurements consist of five concentration levels between 0.01% and 1% protium or deuterium and two residence times. Oxidation is observed to occur between about 550°C and 800°C, with higher levels of conversion achieved at lower temperatures for protium with respect to deuterium at the same volumetric inlet concentration and residence time. Computational fluid dynamics simulations of the experiments were used to customize reaction orders and Arrhenius parameters in a 1-step oxidation mechanism. The trends in the rates for protium and deuterium are extrapolated based on guidance from literature to produce kinetic rate parameters appropriate for tritium oxidation at low concentrations.
LIM1TR (Lithium-Ion Modeling with 1-D Thermal Runaway) is an open-source code that uses the finite volume method to simulate heat transfer and chemical kinetics on a quasi 1-D domain. The target application of this software is to simulate thermal runaway in systems of lithium-ion batteries. The source code for LIM1TR can be found at https://github.com/ajkur/lim1tr. This user guide details the steps required to create and run simulations with LIM1TR starting with setting up the Python environment, generating an input file, and running a simulation. Additional details are provided on the output of LIM1TR as well as extending the code with custom reaction models. This user guide concludes with simple example analyses of common battery thermal runaway scenarios. The corresponding input files and processing scripts can be found in the “Examples” folder in the on-line repository, with select input files included in the appendix of this document.
This work uses accelerating rate calorimetry to evaluate the impact of cell chemistry, state of charge, cell capacity, and ultimately cell energy density on the total energy release and peak heating rates observed during thermal runaway of Li-ion batteries. While the traditional focus has been using calorimetry to compare different chemistries in cells of similar sizes, this work seeks to better understand how applicable small cell data is to understand the thermal runaway behavior of large cells as well as determine if thermal runaway behaviors can be more generally tied to aspects of lithium-ion cells such as total stored energy and specific energy. We have found a strong linear correlation between the total enthalpy of the thermal runaway process and the stored energy of the cell, apparently independent of cell size and state of charge. We have also shown that peak heating rates and peak temperatures reached during thermal runaway events are more closely tied to specific energy, increasing exponentially in the case of peak heating rates.
Energy storage using lithium-ion cells dominates consumer electronics and is rapidly becoming predominant in electric vehicles and grid-scale energy storage, but the high energy densities attained lead to the potential for release of this stored chemical energy. This article introduces some of the paths by which this energy might be unintentionally released, relating cell material properties to the physical processes associated with this potential release. The selected paths focus on the anode–electrolyte and cathode–electrolyte interactions that are of typical concern for current and near-future systems. Relevant material processes include bulk phase transformations, bulk diffusion, surface reactions, transport limitations across insulating passivation layers, and the potential for more complex material structures to enhance safety. We also discuss the development, parameterization, and application of predictive models for this energy release and give examples of the application of these models to gain further insight into the development of safer energy storage systems.
Thermal runaway of Li-ion batteries is a risk that is magnified when stacks of lithium-ion cells are used for large scale energy storage. When limits of propagation can be identified so that systems can be designed to prevent large scale cascading failure even if a failure does occur, these systems will be safer. The prediction of cell-to-cell failure propagation and the propagation limits in lithium-ion cell stacks were studied to better understand and identify safe designs. A thermal-runaway model was considered based on recent developments in thermochemical source terms. Propagating failure was characterized by temperatures above which calorimetry data is available. Results showed high temperature propagating failure predictions are too rapid unless an intra-particle diffusion limit is included, introducing a Damköhler number limiter into the rate expression. This new model form was evaluated against cell-to-cell failure propagation where the end cell of a stack is forced into thermal runaway through a nail-induced short circuit. Limits of propagation for this configuration are identified. Results showed cell-to-cell propagation predictions are consistent with measurements over a range of cell states of charge and with the introduction of metal plates between cells to add system heat capacity representative of structural members. This consistency extends from scenarios where propagation occurs through scenarios where propagation is prevented.
This work demonstrates how staged heat release from layered metal oxide cathodes in the presence of organic electrolytes can be predicted from basic thermodynamic properties. These prediction methods for heat release are an advancement compared to typical modeling approaches for thermal runaway in lithium-ion batteries, which tend to rely exclusively on calorimetry measurements of battery components. These calculations generate useful new insights when compared to calorimetry measurements for lithium cobalt oxide (LCO) as well as the most common varieties of nickel manganese cobalt oxide (NMC) and nickel cobalt aluminum oxide (NCA). Accurate trends in heat release with varying state of charge are predicted for all of these cathode materials. These results suggest that thermodynamic calculations utilizing a recently published database of properties are broadly applicable for predicting decomposition behavior of layered metal oxide cathodes. Aspects of literature calorimetry measurements relevant to thermal runaway modeling are identified and classified as thermodynamic or kinetic effects. The calorimetry measurements reviewed in this work will be useful for development of a new generation of thermal runaway models targeting applications where accurate maximum cell temperatures are required to predict cascading cell-to-cell propagation rates.
Thermal runaway of lithium-ion batteries is a risk that is magnified when stacks of lithium-ion cells are used for large scale energy storage. When limits of propagation can be identified so that systems can be designed to prevent large scale cascading failure even if a failure does occur, these systems will be safer. This work addresses the prediction of cell-to-cell failure propagation and the propagation limits in lithium-ion cell stacks to better understand and identify safe designs. A thermal-runaway model is presented based on recent developments in thermochemical source terms. It is noted that propagating failure is characterized by temperatures above which calorimetry data is available. Results show high temperature propagating failure predictions are too rapid unless an intra-particle diffusion limit is included, introducing a Damköhler number limiter into the rate expression. This new model form is evaluated against cell-to-cell failure propagation where the end cell of a stack is forced into thermal runaway through a nail-induced short circuit. Limits of propagation for this configuration are identified. Results show cell-to-cell propagation predictions are consistent with measurements over a range of cell states of charge and with the introduction of metal plates between cells to add system heat capacity representative of structural members. This consistency extends from scenarios where propagation occurs through scenarios where propagation is prevented.
Accurate models of thermal runaway in lithium-ion batteries require quantitative knowledge of heat release during thermochemical processes. A capability to predict at least some aspects of heat release for a wide variety of candidate materials a priori is desirable. This work establishes a framework for predicting staged heat release from basic thermodynamic properties for layered metal-oxide cathodes. Available enthalpies relevant to thermal decomposition of layered metal-oxide cathodes are reviewed and assembled in this work to predict potential heat release in the presence of alkyl-carbonate electrolytes with varying state of charge. Cathode delithiation leads to a less stable metal oxide subject to phase transformations including oxygen release when heated. We recommend reaction enthalpies and show the thermal consequences of metal-oxide phase changes and solvent oxidation within the battery are of comparable magnitudes. Heats of reaction are related in this work to typical observations reported in the literature for species characterization and calorimetry. The methods and assembled databases of formation and reaction enthalpies in this work lay groundwork a new generation of thermal runaway models based on fundamental material thermodynamics, capable of predicting accurate maximum cell temperatures and hence cascading cell-to-cell propagation rates.
Lithium-ion battery safety is prerequisite for applications from consumer electronics to grid energy storage. Cell and component-level calorimetry studies are central to safety evaluations. Qualitative empirical comparisons have been indispensable in understanding decomposition behavior. More systematic calorimetry studies along with more comprehensive measurements and reporting can lead to more quantitative mechanistic understanding. This mechanistic understanding can facilitate improved designs and predictions for scenarios that are difficult to access experimentally, such as system-level failures. Recommendations are made to improve usability of calorimetry results in mechanistic understanding. From our perspective, this path leads to a more mature science of battery safety.